Macrocyclic picolinamides compounds with fungicidal activity

ABSTRACT

The invention relates to compounds of macrocyclic picolinamides of Formula I suitable to control or prevent growth of fungi.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/885,409, and U.S. Provisional Patent Application Ser. No. 61/885,417, each filed Oct. 1, 2013, the disclosures of each of which is expressly incorporated by reference herein.

BACKGROUND & SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.

The present disclosure relates to macrocyclic picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

One embodiment of the present disclosure may include compounds of Formula I:

-   -   X is H, C(O)R₃, or CH₂OR₃;     -   Y is H, C(O)R₃, or Q;     -   Q is

-   -   R₁ is H, alkyl, alkenyl, aryl, —Si(R₅)₃, —C(O)R₆, each         substituted with 0, 1 or multiple R₆;     -   R₂ is CH₂R₈, aryl, alkyl, alkenyl, each substituted with 0, 1,         or multiple R₆;     -   R₃ is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0,         1, or multiple R₅;     -   R₄ is H, —C(O)R₇ or —CH₂OC(O)R₇;     -   R₅ is alkyl, halo, alkoxy;     -   R₆ is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl,         heterocyclyl, thioalkyl, —C(O)R₅;     -   R₇ is alkyl or alkoxy, each substituted with 0, 1, or multiple         R₆;     -   R₈ is H, alkyl, alkenyl, aryl, heteroaryl, thioalkyl each         substituted with 0, 1, or multiple R₆.

Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.

Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.

It will be understood by the those skilled in the art that the following terms may include generic “R”-groups within their definitions, e.g., “the term alkoxy refers to an —OR substituent”. It is also understood that within the definitions for the following terms, these “R” groups are included for illustration purposes and should not be construed as limiting or being limited by substitutions about Formula I.

The term “alkyl” refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chain containing one or more triple bonds including, but not limited to, propynyl, butynyl and the like.

The term “aryl” refers to any aromatic, mono- or bi-cyclic, containing 0 heteroatoms.

The term “heterocycle” refers to any aromatic or non-aromatic ring, mono- or bi-cyclic, containing one or more heteroatoms

The term “alkoxy” refers to an —OR substituent.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “amino” refers to a —NH₂ substituent.

The term “arylalkoxy” refers to —O(CH₂)_(n)Ar where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl, F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl, F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms, defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

The term thioalkyl refers to an —SR substituent.

Throughout the disclosure, reference to the compounds of Formula I is read as also including diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula (I) is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, and hydroiodide.

It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.

Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.

DETAILED DESCRIPTION

The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural chemical art.

The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.

Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soy bean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.

The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.

Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.

The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. patent application Ser. No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.

The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.

Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluoron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, flpronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.

Additionally, the compounds described herein may be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, fluorochloridone, fluoroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.

The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.

It will be understood by those in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Mycosphaerella graminicola; impect stage: Septoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), barley scald (Rhynchosporium secalis), blast of rice (Magnaporthe grisea), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f sp. tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of beet (Cercospora beticola), early blight of tomato (Alternaria solani), and spot blotch of barley (Cochliobolus sativus). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term “disease-inhibiting and phytologically acceptable amount” refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m²).

Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.

General Schemes

The following schemes illustrate approaches to generating picolinamide compounds of Formula (I). The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.

Compounds of Formula 1.3, where R₂ is as originally defined, can be prepared by the method shown in Scheme 1, steps a-b. Compounds of Formula 1.1, where R₈ is as originally defined and R₉ is alkyl or alkoxy, can be prepared from compounds of Formula 1.0, where R₈ is as originally defined, by treatment with an alkoxy borane such as pinacol borane in the presence of a nickel catalyst, such as bis(cyclooctadiene)nickel(0) (Ni(cod)₂), as described by Ely, R. J.; Morken, J. P. J. Am. Chem. Soc. 2010, 132, 2534-2535, in a solvent such as toluene, and at a temperature between 0 and 23° C. Alternatively, compounds of Formula 1.1, where R₈ is as originally defined and R₉ is alkyl or alkoxy can be prepared as reported in Brown, H. C.; Bhat, K. S.; Randad, R. S. J. Org. Chem. 1989, 54, 1570. Compounds of Formula 1.3, where R₂ is as originally defined, can be prepared from compounds of Formula 1.1, where R₈ is as originally defined and R₉ is as defined above by treatment with a benzyl (Bn) or para-methoxybenzyl (PMB) protected lactate-derived aldehyde such as compound 1.2, prepared as described in Cheng and Brookhart Angew. Chem. Int. Ed. 2012, 51, 9422-9424 (see Takai, K.; Heathcock, C. H. J. Org. Chem. 1985, 50, 3247-3251 for characterization of Bn aldehyde and Terashima et al. Bull. Chem. Soc. Jpn. 1989, 62, 3038-3040 for characterization of PMB aldehyde).

Compounds of Formulas 2.0, 2.1, and 2.2 can be prepared using the methods shown in Scheme 2, steps a-c. Compounds of Formula 2.0, where R₁ is aryl and R₂ is as originally defined, can be prepared by the method shown in a, from compounds of Formula 1.3, where R₂ is as originally defined, by treatment with a triarylbismuth reagent, prepared according to the methods described by Hassan, A. et. al. Organometallics 1996, 15, 5613-5621, Moiseev, D. V. et al. J. Organomet. Chem. 2005, 690, 3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett. 1995, 5, 1035-1038, in the presence of a copper catalyst, such as diacetoxycopper, and an amine base, such as N,N-dicyclohexyl-methylamine, in an aprotic solvent such as toluene at 20-40° C. Compounds of Formula 2.1, where R₁ is alkyl and R₂ is as originally defined, can be prepared from compounds of Formula 1.3, where R₂ is as originally defined, by treatment with a base, such as sodium hydride (NaH), in an aprotic solvent such as tetrahydrofuran (THF), followed by treatment with an alkyl halide or sulfonate, such as isobutyl toluenesulfonate at 0-22° C., as shown in b. Compounds of Formula 2.2, where R₁ is silyl and R₂ is as originally defined, can be prepared from compounds of Formula 1.3, where R₂ is as originally defined, by treatment with a silyl trifluoromethanesulfonate, such as triisopropyl trifluoromethanesulfonate, in the presence of a base, such as 2,6-lutidine, in a solvent such as dichloromethane (CH₂Cl₂, DCM) at a reduced temperature, such as 0° C., as shown in c.

Compounds of Formula 3.2, where R₁ and R₂ are as originally defined and Y is tert-butoxy carbonyl (Boc), can be prepared by the method shown in Scheme 3. Compounds of Formula 3.2 can be prepared from compounds of Formula 3.0, where R₁ and R₂ are as originally defined, by treatment with an alkylborane reagent, such as 9-borabicyclo[3.3.1]nonane (9-BBN), in a solvent such as THF at 20-50° C., followed by treatment with an aqueous base, such as potassium phosphate (K₃PO₄), and a bromoacrylate, such as a compound of Formula 3.1 where Y is Boc, prepared as in Singh et al. Org. Lett. 2003, 17, 3155-3158, and a catalyst, such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (PdCl₂(dppf)) at 20-55° C.

Compounds of Formula 4.0, where R₁ and R₂ are as originally defined and Y is Boc, can be prepared by the method shown in Scheme 4. Compounds of Formula 4.0 can be prepared from compounds of Formula 3.2, where R₁ and R₂ are as originally defined and Y is Boc, by treatment with hydrogen (15-200 psi) in the presence of a catalyst such as 1,2-bis[(2S,5S)-2,5-diethyl-phospholano]benzene(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate ((S,S)-Et-DUPHOS-Rh) in an alcoholic solvent such as methanol (MeOH).

Compounds of Formula 5.3, where R₁ and R₂ are as originally defined and Y is Boc can be prepared through a variety of methods, as shown in Scheme 5, steps a-c. Compounds of Formula 5.0 and 5.1, where R₁ and R₂ are as originally defined and Y is Boc, can be prepared from compounds of Formula 4.0, where R₁ and R₂ are as originally defined, Y is Boc, and the alcohol is protected as the PMB ether, by treatment with an oxidant, such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in an solvent mixture such as DCM and water (H₂O), as shown in a. Compounds of Formula 5.2, where R₁ and R₂ are as originally defined and Y is Boc, can be prepared from compounds of Formula 4.0, where R₁ and R₂ are as originally defined, Y is Boc, and the alcohol is protected as the Bn ether, by hydrogenolysis, i.e., treatment with hydrogen (H₂; 15-500 psi) in the presence of a catalyst, such as 5% or 10% w/w palladium/carbon (Pd/C), in a solvent such as THF, as shown in b. Compounds of Formula 5.3, where R₁ and R₂ are as originally defined and Y is Boc, can be prepared from compounds of Formulas 5.0 and 5.2, where R₁, R₂, and Y are as defined above and the acid is protected as methyl (Me) ester, by treatment with a base such as lithium hydroxide (LiOH) in a mixture of H₂O and a solvent such as THF, as shown in c. Compounds of Formula 5.3, where R₁ and R₂ are as originally defined and Y is Boc, can also be prepared from compounds of Formula 5.1, where R₁, R₂, and Y are as defined above and the acid is protected as the Bn ester, by hydrogenolysis or saponification, as shown in b and c, respectively. Alternatively, compounds of Formula 5.3, where R₁ and R₂ are as originally defined and Y is Boc, can be prepared directly from compounds of Formula 4.0, where R₁, R₂, and Y are as defined above and the alcohol and acid are protected as the Bn ether and Bn ester, respectively, by the hydrogenolysis conditions described in b.

Compounds of Formula 6.0, where R₁ and R₂ are as originally defined and Y is Boc, can be prepared from compounds of Formula 5.3, where R₁ and R₂ are as originally defined and Y is Boc, by the addition of a solution of compounds of Formula 5.3 in a halogenated solvent such as DCM or an aromatic solvent such as toluene to a mixture of a base, such as DMAP, and an anhydride, such as 2-methyl-6-nitrobenzoic anhydride (MNBA), in either a halogenated solvent such as DCM or an aromatic solvent such as toluene over a period of 4-12 hours, as shown in Scheme 6.

Compounds of Formula 7.1 can be prepared according to the methods shown in Scheme 7, steps a-b. Compounds of Formula 7.0, where R₁ is triisopropylsilyl (TIPS), R₂ is as originally defined, Y is Boc, and X is methoxymethyl (MOM) can be prepared from compounds of Formula 6.0, where R₁, R₂, and Y are as defined above, by treatment with an aldehyde, such as paraformaldehyde, in a solvent such as DCM in the presence of a silyl chloride, such as trimethylsilyl chloride, at a reduced temperature such as 0° C., followed by addition of a solution of a base such as triethylamine, in an alcoholic solvent such as methanol, as shown in a. Compounds of Formula 7.1, where R₁ is H and R₂, X, and Y are as defined above, can be prepared from compounds of Formula 7.0, where R₁, R₂, X, and Y are as defined above, by treatment with a fluoride salt such as tetra-N-butylammonium fluoride (TBAF), in a solvent such as THF, as shown in b.

Compounds of Formulas 8.0-8.8 can be prepared through the methods shown in Scheme 8, steps a-g. Compounds of Formula 8.0, where R₁ is allyloxy, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 7.1, where R₁ is H, R₂, X, and Y are as defined above, by treatment with an allyl carbonate, such as a tert-butyl (allyl) carbonate or a symmetric (allyl) carbonate, such as bis(2-methylallyl) carbonate, in the presence of a palladium catalyst and ligand, for example tris(dibenzylideneacetone)-dipalladium(0) (Pd₂(dba)₃) and 1,1′-bis(diphenylphosphino)ferrocene (dppf), in a polar aprotic solvent like tetrahydrofuran (THF) at an elevated temperature such as 60° C., as shown in a. Compounds of Formula 8.1, where R₁ is alkyl, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 8.0, where R₁, R₂, X, and Y are defined as above, by treatment with H₂ (15-200 psi) in the presence of a catalyst, such as 5% or 10% w/w Pd/C in a solvent such as EtOAc, as shown in b. Compounds of Formula 8.2, where R₁ is an aliphatic aldehyde and R₂, X, and Y are as defined above, can be prepared from compounds of Formula 8.0, where R₁, R₂, X, and Y are as defined above, by treatment with ozone in the presence of a base, such as sodium bicarbonate (NaHCO₃) in a mixture of a halogenated and an alcoholic solvent, such as DCM and MeOH, as shown in c. Compounds of Formula 8.3, where R₁ is fluorinated alkyl and R₂, X, and Y are as defined above, can be prepared from compounds of Formula 8.2, where R₁, R₂, X, and Y are as defined above, by treatment with a fluorinating reagent, such as bis(2-methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor®) in a solvent such as DCM, as shown in d.

Compounds of Formula 8.4, where R₁ is an vinylogous ester, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 7.1, where R₁ is H, R₂, X, and Y are as defined above, by treating solutions of the compounds of Formula 7.1 in a solvent such as DCM with a catalytic amount of 1,4-diazabicyclo[2.2.2]octane (DABCO), followed by addition of a conjugated alkyne, such as but-3-yn-2-one at a reduced temperature, for example 0° C., as shown in e. Compounds of Formula 8.5, where R₁ is an aliphatic ketone, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 8.4, where R₁, R₂, X, and Y are as defined above, by the reductive conditions described in b. Compounds of Formula 8.6, where R₁ is fluorinated alkyl, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 8.5, where R₁, R₂, X, and Y are defined as above, by the fluorination conditions described in d.

Compounds of Formula 8.7, where R₁ is acyl, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 7.1, where R₁ is H, R₂ is as originally defined, X is MOM, and Y is Boc, by treatment with a base such as triethylamine and a catalyst such as (DMAP) in a solvent such as DCM, followed by treatment with an acid chloride, as shown in f.

Compounds of Formula 8.8, where R₁ is alkyl, R₂ is as originally defined, X is MOM, and Y is Boc, can be prepared from compounds of Formula 7.1, where R₁ is H, R₂ is as originally defined, X is MOM, and Y is Boc, by treatment with a base, such as 1,8-bis(dimethylamino)naphthalene (Proton Sponge®) and an alkylating agent, such as trimethyloxonium tetrafluoroborate, in a solvent such as DCM, as shown in g.

Compounds of Formula 9.1, where R₁ is as originally defined and Y is Boc, can be prepared by the method shown in Scheme 9. Compounds of Formula 9.1 can be prepared from compounds of Formula 9.0, where R₁ is as originally defined and Y is Boc, by treatment with a fluoride salt, such as TBAF, in a solvent such as THF.

Compounds of Formulas 10.0-10.7 can be prepared through the methods shown in Scheme 10, steps a-h. Compounds of Formula 10.0, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 9.1, where R₁ is as originally defined and Y is Boc, by treatment with a triarylbismuth reagent, prepared according to the methods described by Hassan, A. et. al. Organometallics 1996, 15, 5613-5621, Moiseev, D. V. et al. J. Organomet. Chem. 2005, 690, 3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett. 1995, 5, 1035-1038, in the presence of a copper catalyst, such as diacetoxycopper, and an amine base, such as N,N-dicyclohexyl-methylamine, in an aprotic solvent such as toluene at an elevated temperature of about 50° C., as shown in a. Compounds of Formula 10.1, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 9.1, where R₁ and Y are as defined above, by treatment with a base such as Proton Sponge® followed by an alkylating agent, such as trimethyloxonium tetrafluoroborate, in a solvent such as DCM, as shown in b. Compounds of Formula 10.2, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 9.1, where R₁ and Y are as defined above, by treatment with an oxidizing reagent, such as Dess-Martin periodinane, in a solvent such as DCM, as shown in c. Compounds of Formula 10.3, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 10.2, where R₁ and Y are as defined above, by treatment with a fluorinating reagent, such as Deoxo-Fluor®, in a solvent such as DCM, as shown in d. Compounds of Formula 10.4, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 9.1, where R₁ and Y are as defined above, by treatment with a fluorinating reagent, such as Deoxo-Fluor®, in a solvent such as DCM or through halogenation conditions, such as treatment with perhalomethanes in the presence of triphenylphosphine in DCM at a reduced temperature, such as 0° C., as shown in e. Compounds of Formula 10.5, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 10.4, where R₁ and Y are as defined above, by treatment with a reducing agent such as tributyltin hydride in the presence of a radical initiator, such as azobisisobutyronitrile (AIBN), in a solvent such as toluene at an elevated temperature, for example 80° C., as shown in f. Compounds of Formula 10.6, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 9.1, where R₁ and Y are as defined above, by treatment with a selenocyanate and a phosphine, such as tributylphosphine, in a solvent such as THF at a temperature from about 0° C. to about 23° C., as shown in g. Compounds of Formula 10.7, where R₁ is as originally defined and Y is Boc, can be prepared from compounds of Formula 10.6, where R₁ and Y are as defined above, by treatment with an oxidizing agent, such as hydrogen peroxide, in a solvent such as THF, as shown in h.

Compounds of Formulas 11.4 and 11.5 can be prepared through the methods shown in Scheme 11, steps a-d. Compounds of Formula 11.4, where R₁ and R₂ are as originally defined, can be prepared from a variety of precursors, including, but not limited to, compounds of Formulas 11.0, 11.1, 11.2, and 11.3, where R₁ and R₂ are as originally defined, and Y is Boc (11.0), X and Y are Boc (11.1), X is MOM and Y is Boc (11.2), and Y is CBz (11.3) respectively. Treating compounds of Formulas 11.0-11.2 with an acid, such as a 4.0 M hydrogen chloride (HCl) solution in dioxane, in a solvent such as DCM affords the hydrochloride salt of compounds of Formula 11.4, which may be neutralized in situ in step d or neutralized prior to use to give the free amine, as shown in a. Additionally, compounds of Formula 11.4, where R₁ and R₂ are as originally defined, can be prepared from compounds of Formulas 11.0 and 11.1, where R₁, R₂, X, and Y are as originally defined, by treatment with trimethylsilyl trifluoromethanesulfonate in the presence of a base, such 2,6-lutidine, in an aprotic solvent such as DCM, followed by treatment with a protic solvent such as MeOH, as shown in b. Alternatively, compounds of Formula 11.4, where R₁ and R₂ are as originally defined, can be prepared from compounds of Formula 11.3, where R₁ and R₂ are as originally defined and Y is CBz, by treatment with hydrogen in the presence of a catalyst, such as 5% or 10% w/w Pd/C, in a solvent such as EtOAc, as shown in c. Compounds of Formula 11.5, where R₁ and R₂ are as originally defined, can be prepared from compounds of Formula 11.4, where R₁ and R₂ are as originally defined, by treatment with 3-hydroxy-4-methoxypicolinic acid in the presence of an amine base, such as 4-methylmorpholine or triethylamine (TEA), and a peptide coupling reagent, such as O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (HATU) or benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), in an aprotic solvent such as DCM, as shown in d.

Compounds of Formula 12.0, where R₁, R₂ and R₄ are as originally defined, can be prepared by the method shown in Scheme 12. Compounds of Formula 12.0 can be prepared from compounds of Formula 11.5, where R₁ and R₂ are as originally defined, by treatment with the appropriate alkyl halide with or without a reagent such as sodium iodide (NaI) and an alkali carbonate base such as sodium carbonate (Na₂CO₃) or potassium carbonate (K₂CO₃) in a solvent such as acetone or by treatment with an acyl halide in the presence of an amine base, such as pyridine, triethylamine, DMAP, or mixtures thereof in an aprotic solvent such as DCM, as shown in a.

Compounds of Formula 13.0, where R₁ and R₄ are as originally defined and R₂ is cyclohexyl optionally substituted with one or multiple R₁₀, wherein R₁₀ is halo or alkyl, can be prepared by the method shown in Scheme 13. Compounds of Formula 13.0 can be prepared from compounds of Formula 12.0, where R₁ and R₄ are as originally defined and R₂ is aryl optionally substituted with one or multiple R₁₀, wherein R₁₀ is halo or alkyl, by treatment with hydrogen gas in the presence of a catalyst, such as rhodium on carbon (Rh/C), in a solvent such as THF at an elevated temperature such as 70° C., as shown in a.

The following examples are presented to illustrate the various aspects of the compounds of the present disclosure and should not be construed as limitations to the claims.

EXAMPLES Example 1 Step 1: Preparation of (2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol

Under a strict nitrogen atmosphere an oven-dried round-bottomed flask with a magnetic stir bar was charged with bis(1,5-cyclooctadiene)nickel(0) (0.297 grams (g), 1.080 millimole (mmol)) and tricyclohexylphosphine (0.379 g, 1.35 mmol). Anhydrous toluene (40 milliliters (mL)) followed by 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.34 ml, 57.5 mmol) and (E)-6-methylhepta-1,3-diene (11.9 g, 54.0 mmol), prepared according to the procedure disclosed in Wang, Y.; West, F. G. Synthesis 2002, 99-103, were added to the flask and the reaction was allowed to stir at room temperature for 20 hours (h), as described in the diene hydroboration conditions reported in Ely, R. J.; Morken, J. P. J. Am. Chem. Soc. 2010, 132, 2534-2535. To the mixture was added a solution of (S)-2-((4-methoxybenzyl)oxy)propanal (10.49 g, 54.0 mmol) in anhydrous toluene (5 mL) at −20° C. The reaction mixture was slowly warmed to room temperature and stirred at room temperature for 40 h, then quenched with MeOH and stirred for an additional 2 h. The crude mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (SiO₂; gradient, hexanes/ethyl acetate) to yield the title compound as a colorless oil (11.3 g, 69%): IR (neat) 3467, 2925, 2868, 1513, 1247 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.27-7.22 (m, 2H), 6.90-6.85 (m, 2H), 5.51-5.38 (m, 1H), 5.08-4.96 (m, 2H), 4.52-4.40 (m, 2H), 3.80 (s, 3H), 3.66 (ddd, J=9.2, 3.1, 2.1 Hz, 1H), 3.59-3.49 (m, 1H), 2.26-2.20 (m, 1H), 2.04-1.95 (m, 1H), 1.90-1.80 (m, 1H), 1.59-1.43 (m, 1H), 1.29-1.14 (m, 2H), 1.13 (d, J=6.2 Hz, 3H), 1.10-0.99 (m, 1H), 0.87 (d, J=6.4 Hz, 3H), 0.86 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 159.19, 138.56, 130.59, 129.22, 116.59, 113.82, 75.89, 74.46, 70.11, 55.29, 47.18, 36.05, 28.57, 28.23, 22.98, 22.42, 12.17; ESIMS m/z 329.2 ([M+Na]⁺).

Example 1 Step 2a: Preparation of 1-methoxy-4-((((2S,3R,4S)-7-methyl-3-phenoxy-4-vinyloctan-2-yl)oxy)methyl)benzene

To a solution of (2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g, 6.53 mmol) in anhydrous toluene (30 mL) was added bis(acetato-O)triphenylbismuth(V) (5.47 g, 9.79 mmol), N-cyclohexyl-N-methylcyclohexanamine (2.10 mL, 9.79 mmol) and anhydrous diacetoxycopper (0.237 g, 1.305 mmol) at room temperature. The reaction was heated at 43° C. for 5 h, filtered through a Celite® pad, concentrated and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a colorless oil (2.30 g, 92%): ¹H NMR (400 MHz, CDCl₃) δ 7.27-7.21 (m, 2H), 7.19-7.13 (m, 2H), 7.03-6.97 (m, 2H), 6.94-6.88 (m, 1H), 6.86-6.81 (m, 2H), 5.64-5.51 (m, 1H), 5.07-5.00 (m, 2H), 4.54-4.33 (m, 2H), 4.26 (dd, J=6.5, 4.7 Hz, 1H), 3.79 (s, 3H), 3.79-3.72 (m, 1H), 2.44-2.31 (m, 1H), 1.74-1.61 (m, 1H), 1.52-1.38 (m, 1H), 1.34-1.25 (m, 1H), 1.23 (d, J=6.3 Hz, 3H), 1.22-1.11 (m, 1H), 1.09-0.98 (m, 1H), 0.84 (d, J=6.8 Hz, 3H), 0.82 (d, J=6.8 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 160.05, 159.04, 139.48, 129.42, 129.32, 129.19, 121.56, 120.67, 116.46, 113.67, 83.41, 75.26, 70.16, 55.26, 47.15, 36.47, 28.05, 27.64, 22.96, 22.34, 14.83; ESIMS m/z 405.3 ([M+Na]⁺).

Example 1 Step 2b: Preparation of 1-((((2S,3R,4S)-3-(cyclopropylmethoxy)-7-methyl-4-vinyloctan-2-yl)oxy)methyl)-4-methoxybenzene

A solution of (2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g, 6.53 mmol) in anhydrous DMF (12 mL) was added at room temperature to a solution of NaH (NaH; 0.326 g, 8.16 mmol, 60% dispersion in mineral oil) in anhydrous DMF (12 ml). The reaction was stirred for 15 minutes (min) at room temperature, treated with (bromomethyl)cyclopropane (0.823 ml, 8.48 mmol) at room temperature, and then was heated to 40° C. for and stirred for 6 h. The reaction was cooled to room temperature and additional NaH (0.131 g, 3.27 mmol) and (bromomethyl)cyclopropane (0.317 mL, 3.27 mmol) were added, and the reaction was heated at 45° C. for 4 h. The reaction was again cooled to room temperature and a third batch of NaH (0.131 g, 3.27 mmol) followed by (bromomethyl)cyclopropane (0.317 mL, 3.27 mmol) was added and the reaction was heated at 45° C. for 2 h. The reaction mixture was quenched with saturated aqueous ammonium chloride (NH₄Cl) and the phases were separated. The aqueous phase was extracted with diethyl ether (Et₂O), and the combined organic phases were washed with brine, dried over magnesium sulfate (MgSO₄), concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a colorless oil (1.94 g, 82%): IR (neat) 2953, 2868, 1613, 1513, 1247, 1084 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.25-7.20 (m, 2H), 6.89-6.81 (m, 2H), 5.52 (dt, J=17.0, 10.0 Hz, 1H), 5.03-4.92 (m, 2H), 4.52-4.32 (m, 2H), 3.78 (s, 3H), 3.65-3.56 (m, 2H), 3.34 (dd, J=10.0, 6.9 Hz, 1H), 3.28-3.22 (m, 1H), 2.09 (tdd, J=10.1, 7.7, 3.1 Hz, 1H), 1.81-1.67 (m, 1H), 1.55-1.42 (m, 1H), 1.28-1.13 (m, 2H), 1.19 (d, J=6.3 Hz, 3H), 1.13-0.95 (m, 2H), 0.87 (d, J=6.4 Hz, 3H), 0.86 (d, J=6.8 Hz, 3H), 0.56-0.45 (m, 2H), 0.25-0.14 (m, 2H); ESIMS m/z 383.4 ([M+Na]⁺).

Example 1 Step 2b: Preparation of 1-((((2S,3R,4S)-3-isobutoxy-7-methyl-4-vinyloctan-2-yl)oxy)methyl)-4-methoxybenzene

A solution of (2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g, 6.53 mmol) in anhydrous DMF (15 mL) was added at room temperature to a solution of NaH (0.326 g, 8.16 mmol, 60% dispersion in mineral oil) in anhydrous DMF (6.0 mL). The reaction was stirred for 15 min at room temperature, then isobutyl 4-methylbenzenesulfonate (1.66 mL, 8.16 mmol) was added at room temperature and the reaction was heated at 50° C. and stirred for 1 h. The reaction was cooled down to room temperature and NaH (0.261 g, 6.53 mmol) followed by isobutyl 4-methylbenzenesulfonate (1.33 mL, 6.53 mmol) were added and heating continued for 2 h at 50° C., after which the reaction was again cooled down to room temperature and a third batch of NaH (0.131 g, 3.27 mmol) and isobutyl 4-methylbenzenesulfonate (0.67 mL, 3.27 mmol) were added and the reaction was heated at 50° C. for 7 h. The reaction mixture was quenched with saturated NH₄Cl and the phases were separated. The aqueous phase was extracted with Et₂O, and the combined organic phases were washed with brine, dried over MgSO₄, concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a colorless oil (2.05 g, 87%): ¹H NMR (400 MHz, CDCl₃) δ 7.29-7.21 (m, 2H), 6.90-6.83 (m, 2H), 5.61-5.49 (m, 1H), 5.04-4.89 (m, 2H), 4.53-4.33 (m, 2H), 3.80 (s, 3H), 3.64-3.51 (m, 2H), 3.28-3.16 (m, 2H), 2.15-2.02 (m, 1H), 1.90-1.77 (m, 1H), 1.76-1.60 (m, 1H), 1.54-1.41 (m, 1H), 1.28-1.11 (m, 2H), 1.17 (d, J=6.3 Hz, 3H), 1.08-0.96 (m, 1H), 0.95-0.88 (m, 6H), 0.86 (d, J=6.4 Hz, 3H), 0.85 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 158.97, 140.43, 131.09, 129.06, 115.66, 113.67, 84.26, 79.58, 76.41, 70.05, 55.26, 47.38, 36.46, 29.13, 28.21, 27.85, 22.91, 22.47, 19.66, 19.55, 14.25; ESIMS m/z 385.4 ([M+Na]⁺).

Example 1 Step 2b: Preparation of 1-((2S,3R,4S)-3-(benzyloxy)-4-((4-methoxy-benzyl)oxy)-2-vinylpentyl)-2,4-difluorobenzene

An oven-dried 100 mL Schlenk flask was cooled under nitrogen and was then charged with NaH (60% dispersion in mineral oil, 1.24 g, 31.0 mmol) and anhydrous DMF (50 mL). A solution of (2S,3R,4S)-4-(2,4-difluorobenzyl)-2-((4-methoxybenzyl)oxy)hex-5-en-3-ol (8.06 g, 22.2 mmol) in anhydrous DMF (10 mL) was added via canula over a period of 6 min followed by an anhydrous DMF rinse (5 mL) of the source flask and needle. Gas evolution was observed, and the resulting white suspension was stirred at room temperature for 90 min, at which point the reaction color had turned red. Benzyl bromide (4.23 mL, 35.6 mmol) was added and the reaction was heated to 40° C. After stirring for 3 hours, the heat source was removed and the reaction was cooled to room temperature. Saturated aqueous NH₄Cl solution (20 mL) was added, and the mixture was allowed to stir for 30 min, at which point gas evolution had ceased. The crude mixture was then diluted with H₂O (50 mL) and extracted with Et₂O (100 mL×3). The combined organic extracts were washed with saturated aqueous NH₄Cl solution (100 mL), dried over anhydrous MgSO₄, filtered, concentrated, and the residue was purified by column chromatography on SiO₂ (0%→10% methyl tert-butylether (MTBE)/hexane gradient) to furnish the title product as white solid (90% Pure, 8.47 g, 84%): mp 141-144° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.30 (m, 4H), 7.30-7.24 (m, 3H), 7.05-6.96 (m, 1H), 6.90-6.84 (m, 2H), 6.76-6.67 (m, 2H), 5.57 (dddd, J=17.1, 10.3, 9.0, 1.3 Hz, 1H), 4.88 (dd, J=10.2, 1.9 Hz, 1H), 4.87 (d, J=11.4 Hz, 1H), 4.72 (ddd, J=17.2, 1.8, 0.5 Hz, 1H), 4.63 (d, J=11.4 Hz, 1H), 4.53 (d, J=11.3 Hz, 1H), 4.40 (d, J=11.3 Hz, 1H), 3.79 (s, 3H), 3.70 (qd, J=6.2, 3.8 Hz, 1H), 3.52 (dd, J=6.9, 3.9 Hz, 1H), 3.09 (d, J=10.4 Hz, 1H), 2.59-2.44 (m, 2H), 1.25 (d, J=6.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 161.24 (dd, J=245.7, 11.9 Hz), 161.09 (dd, J=247.0, 11.6 Hz), 159.11, 138.90, 138.24, 132.05 (dd, J=9.4, 6.7 Hz), 130.92, 129.17, 128.33, 127.97, 127.53, 123.45 (dd, J=15.9, 3.7 Hz), 116.95, 113.78, 110.59 (dd, J=20.8, 3.7 Hz), 103.33 (dd, J=26.5, 25.0 Hz), 83.67, 76.56, 74.18, 70.41, 55.28, 47.98, 29.75, 14.24; ¹⁹F NMR (376 MHz, CDCl₃) δ −113.06 (d, J=6.8 Hz), −113.95 (d, J=6.4 Hz); ESIMS: m/z 475 ([M+Na]⁺).

Example 1 Step 2b: Preparation of 1-((((2S,3R,4S)-4-benzyl-3-(2-methoxyethoxy)-hex-5-en-2-yl)oxy)methyl)-4-methoxybenzene

To a suspension of NaH (0.088 g, 3.68 mmol) in DMF (10 mL) was added dropwise a solution of (2S,3R,4S)-4-benzyl-2-((4-methoxybenzyl)oxy)hex-5-en-3-ol (1 g, 3.06 mmol) in DMF (5 mL). The mixture was stirred at room temperature for 20 min and then 1-bromo-2-methoxyethane (0.852 g, 6.13 mmol) was added. The reaction mixture was heated to 60° C. for 5 h. The reaction was cooled to room temperature and another portion of NaH (0.088 g, 3.68 mmol) and 1-bromo-2-methoxyethane (0.852 g, 6.13 mmol) were added, and the reaction mixture was heated to 60° C. and stirred overnight. The reaction mixture was quenched with saturated NH₄Cl and the phases were separated. The aqueous phase was extracted with EtOAc (2×40 mL), and the combined organic phases were dried over MgSO₄, concentrated, and purified by column chromatography on SiO₂ (EtOAc/hexanes) to furnish the title product as colorless oil (0.730 g, 62%): ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.06 (m, 7H), 6.86 (dd, J=8.6, 0.9 Hz, 2H), 5.68-5.47 (m, 1H), 4.95-4.69 (m, 2H), 4.60-4.26 (m, 2H), 4.04-3.91 (m, 1H), 3.79 (s, 3H), 3.73-3.69 (m, 1H), 3.68-3.60 (m, 1H), 3.59-3.53 (m, 2H), 3.39 (d, J=0.8 Hz, 3H), 3.38-3.36 (m, 1H), 3.15 (d, J=10.4 Hz, 1H), 2.70-2.42 (m, 2H), 1.30-1.17 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 159.05, 140.67, 138.83, 130.95, 129.56, 129.11, 127.92, 125.60, 116.61, 113.74, 84.59, 76.46, 72.41, 71.76, 70.26, 58.96, 55.28, 48.55, 36.96, 14.01; ESIMS m/z 407.2 ([M+Na]⁺).

Example 1 Step 2c: Preparation of triisopropyl(((2S,3R,4S)-2-((4-methoxybenzyl)-oxy)-7-methyl-4-vinyloctan-3-yl)oxy)silane

To an ice-cooled solution of (2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (3.70 g, 12.07 mmol) in anhydrous CH₂Cl₂ (60.4 ml) were added 2,6-dimethylpyridine (1.97 ml, 16.9 mmol) and triisopropylsilyl trifluoromethanesulfonate (3.89 ml, 14.5 mmol), and the mixture was allowed to warm to room temperature while stirring overnight. The reaction mixture was poured into saturated aqueous sodium bicarbonate (NaHCO₃) solution and mixed thoroughly. The phases were separated and the aqueous phase was extracted with CH₂Cl₂, and the combined organic phases were washed with brine, dried over MgSO₄, concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a colorless oil (4.76 g, 85%): ¹H NMR (400 MHz, CDCl₃) δ 7.26-7.19 (m, 2H), 6.88-6.81 (m, 2H), 5.63-5.50 (m, 1H), 5.05-4.89 (m, 2H), 4.51-4.29 (m, 2H), 3.84 (dd, J=6.6, 3.0 Hz, 1H), 3.79 (s, 3H), 3.55-3.46 (m, 1H), 2.11-1.98 (m, 1H), 1.75-1.61 (m, 1H), 1.56-1.41 (m, 1H), 1.24-1.17 (m, 1H), 1.15 (d, J=6.2 Hz, 3H), 1.13-0.97 (m, 20H), 0.85 (d, J=6.8 Hz, 3H), 0.84 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 158.88, 139.86, 131.19, 129.19, 115.64, 113.50, 78.34, 76.39, 70.08, 55.24, 49.46, 36.94, 28.35, 28.23, 22.83, 22.51, 18.43, 18.41, 13.71, 13.18; ESIMS m/z 485.4 ([M+Na]⁺).

Example 1 Step 3: Preparation of (6R,7R,8S,Z)-benzyl 2-((tert-butoxycarbonyl)amino)-7-(cyclopropylmethoxy)-6-(4-fluorobenzyl)-8-((4-methoxybenzyl)-oxy)non-2-enoate

A 0.5 M solution of 9-borabicyclo[3.3.1]nonane in anhydrous THF (7.0 mL, 3.50 mmol) was added to a solution of 1-((2S,3R,4S)-3-(cyclopropylmethoxy)-4-((4-methoxybenzyl)oxy)-2-vinylpentyl)-4-fluorobenzene (960 milligrams (mg), 2.409 mmol) in anhydrous THF (5 mL) at 0° C. The resulting solution was warmed to room temperature and stirred for 1 h, then heated to 50° C. for 2 h. The reaction was cooled to room temperature, a solution of K₃PO₄ (3 M aqueous, 1.61 mL, 4.82 mmol) was added, and the reaction was stirred for 15 min at room temperature. To the mixture was added a solution of (Z)-benzyl 3-bromo-2-((tert-butoxycarbonyl)amino)acrylate (870 mg, 2.44 mmol), prepared using a similar procedure to that disclosed in Singh, J. et al. Org. Lett. 2003, 5, 3155-3158, in degassed DMF (2 mL) and PdCl₂(dppf) (88.0 mg, 0.120 mmol). The reaction was heated overnight at 60° C., cooled, diluted with Et₂O, and washed with saturated aqueous NaHCO₃. The phases were separated and the aqueous phase was extracted with Et₂O. The combined organic phases were washed with saturated aqueous NH₄Cl and water, dried over MgSO₄, concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a pale yellow oil (1.43 g, 88%): ¹H NMR (400 MHz, CDCl₃) δ 7.38-7.26 (m, 5H), 7.26-7.19 (m, 2H), 6.97-6.89 (m, 2H), 6.88-6.78 (m, 4H), 6.39 (t, J=7.2 Hz, 1H), 6.29 (s, 1H), 5.24-5.10 (m, 2H), 4.61-4.25 (m, 2H), 3.73 (s, 3H), 3.64-3.53 (m, 1H), 3.45-3.31 (m, 2H), 3.22 (dd, J=7.2, 2.8 Hz, 1H), 2.79 (dd, J=14.0, 4.8 Hz, 1H), 2.37 (dd, J=14.0, 9.5 Hz, 1H), 2.25-2.08 (m, 2H), 1.92-1.79 (m, 1H), 1.57-1.43 (m, 1H), 1.43 (s, 9H), 1.39-1.28 (m, 1H), 1.28 (d, J=6.0 Hz, 3H), 1.09-0.96 (m, 1H), 0.53-0.44 (m, 2H), 0.21-0.13 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 164.48, 160.91 (d, J=243.2 Hz), 158.99, 153.40, 136.94 (d, J=3.2 Hz), 136.82, 135.55, 130.26, 130.24 (d, J=7.7 Hz), 129.39, 128.31, 128.04, 128.00, 126.23, 114.62 (d, J=20.9 Hz), 113.58, 82.58, 80.01, 76.69, 74.41, 69.70, 66.72, 54.94, 40.81, 34.83, 28.49, 27.99, 25.75, 16.00, 11.01, 2.86, 2.78; ¹⁹F NMR (376 MHz, CDCl₃) δ −117.70; ESIMS m/z 676.4 ([M+H]⁺).

Example 1 Step 4: (2S,6R,7R,8S)-methyl-2-((tert-butoxycarbonyl)amino)-6-(4-methoxybenzyl)-8-((4-methoxybenzyl)oxy)-7-((triisopropylsilyl)oxy)nonanoate

The title compound was prepared using a procedure adapted from Jones et al. Tetrahedron Lett. 1999, 40, 1211-1214. A high pressure reactor was charged with (6R,7R,8S,Z)-methyl 7-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-8-((4-methoxybenzyl)oxy)-6-(4-methylbenzyl)non-2-enoate (2.72 g, 3.82 mmol) and anhydrous MeOH (20 mL) and the solution was sparged with nitrogen using a needle for 10 min. To the solution was added (+)-1,2-bis((2S,5S)-2,5-diethylphospholano)benzene-(cyclooctadiene)rhodium(I) trifluoromethanesulfonate (28 mg, 0.038 mmol) and the reactor was sealed, pressurized with H₂ (200 psi) and stirred at room temperature for 3 h. The pressure was released and the crude reaction mixture was filtered through a pad of Celite®, concentrated, and purified by column chromatography on SiO₂ (0→100% EtOAc/hexanes gradient) to furnish the title product as a colorless oil (2.73 g, 100%): IR (neat) 3377, 2941, 2865, 1744, 1715, 1511, 1245, 1164 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.31-7.22 (m, 2H), 7.01 (d, J=8.5 Hz, 2H), 6.87 (d, J=8.6 Hz, 2H), 6.77 (d, J=8.6 Hz, 2H), 4.90 (d, J=8.5 Hz, 1H), 4.51 (d, J=11.2 Hz, 1H), 4.33 (d, J=11.3 Hz, 1H), 4.25 (q, J=7.2 Hz, 1H), 3.81 (s, 3H), 3.78 (s, 3H), 3.70 (s, 3H), 3.63-3.52 (m, 1H), 2.77 (dd, J=13.8, 7.2 Hz, 1H), 2.43 (dd, J=13.8, 7.4 Hz, 1H), 1.78 (d, J=7.7 Hz, 1H), 1.70 (s, 1H), 1.52 (d, J=10.7 Hz, 2H), 1.44 (s, 9H), 1.35-1.07 (m, 7H), 1.07-0.93 (m, 21H); ¹³C NMR (101 MHz, CDCl₃) δ 173.40, 158.94, 157.67, 155.35, 133.91, 131.04, 130.15, 129.21, 113.63, 113.58, 79.80, 76.44, 76.36, 70.18, 55.29, 55.26, 53.37, 52.16, 45.89, 36.12, 33.12, 29.50, 28.32, 23.81, 18.27, 16.23, 13.02; HRMS-ESI (m/z) ([M]⁺) calcd for C₄₀H₆₅NO₈Si, 715.448. found, 715.4479.

Example 1 Step 5a: Preparation of (2S,6R,7R,8S)-methyl 2-((tert-butoxycarbonyl)-amino)-8-hydroxy-7-isobutoxy-6-(2-(methylthio)ethyl)nonanoate

To a mixture of (2S,6R,7R,8S)-methyl 2-((tert-butoxycarbonyl)amino)-7-isobutoxy-8-((4-methoxybenzyl)oxy)-6-(2-(methylthio)ethyl)nonanoate (536 mg, 0.941 mmol) and 0.85 mL H₂O in CH₂Cl₂ (9.4 mL) at 0° C. (icewater bath) was added DDQ (214 mg, 0.941 mmol). The resulting dark mixture was stirred at 0° C. for 3 h, then another portion of DDQ (41 mg, 0.180 mmol) were added and the reaction was stirred for 1 h. The reaction was quenched with sodium hydroxide (NaOH; 1.3 ml of 1M aqueous, 1.3 mmol) and stirred for 10 min. The reaction was then diluted with H₂O (20 mL) and extracted with CH₂Cl₂ (3×20 mL). The combined organic extracts were dried over Na₂SO₄, filtered, and concentrated to provide a red oil which was purified by column chromatography on SiO₂ (5→35% acetone/hexanes gradient) to furnish the title product as a clear, colorless oil (353 mg, 83%): ¹H NMR (400 MHz, CDCl₃) δ 5.02 (d, J=8.0 Hz, 1H), 4.31 (d, J=5.2 Hz, 1H), 3.95-3.83 (m, 1H), 3.74 (d, J=1.6 Hz, 3H), 3.36 (dd, J=8.5, 6.3 Hz, 1H), 3.22 (dd, J=8.5, 6.6 Hz, 1H), 3.05 (dd, J=5.6, 3.9 Hz, 1H), 2.58 (ddd, J=14.0, 8.7, 5.3 Hz, 1H), 2.47 (ddd, J=12.8, 8.3, 7.4 Hz, 1H), 2.10 (s, 3H), 1.96-1.68 (m, 4H), 1.68-1.49 (m, 3H), 1.45 (s, 9H), 1.39 (s, 4H), 1.21 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 1.9 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 173.36, 155.36, 84.83, 79.93, 79.24, 68.10, 53.20, 52.27, 38.01, 33.20, 33.05, 32.76, 30.90, 29.21, 28.83, 28.33, 22.83, 19.52, 19.46, 19.11, 15.43; ESIMS m/z 450.4 ([M+H]+), 472.4 ([M+Na]⁺).

Example 1 Step 5b: Preparation of (2S,6R,7R,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxy-6-(4-methylbenzyl)-7-phenoxynonanoic acid

A 25 mL screw top vial was charged with (2S,6R,7R,8S)-benzyl 8-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-6-(4-methylbenzyl)-7-phenoxynonanoate (741 mg, 1.11 mmol), EtOAc (10 mL), and 10% Pd/C (61 mg, 0.057 mmol). The vial was sealed with a septum-cap, and the reaction was briefly degassed under high vacuum, and then repressurized under about 1 atmosphere of H₂ (balloon pressure). This process was repeated 2×, and the reaction was stirred at room temperature under balloon pressure of hydrogen. After stirring for 19 h, the solids were removed by filtration through a pad of Celite®, rinsing with excess EtOAc. The filtrate was concentrated and then dried under high vacuum to afford the title compound as a white solid (516 mg, 91%): mp 48-51° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.17 (m, 2H), 7.09 (s, 4H), 6.97-6.83 (m, 3H), 6.69-6.02 (m, 2H), 5.00 (d, J=8.3 Hz, 1H), 4.33-3.96 (m, 3H), 3.03 (dd, J=13.8, 5.3 Hz, 1H), 2.49 (dd, J=13.9, 8.9 Hz, 1H), 2.33 (s, 3H), 2.19-2.08 (m, 1H), 1.78-1.62 (m, 1H), 1.59-1.15 (m, 17H); ¹³C NMR (101 MHz, CDCl₃) δ 176.73, 159.43, 155.73, 138.03, 135.33, 129.57, 129.10, 129.06, 120.88, 115.85, 82.16, 80.24, 68.15, 53.26, 41.47, 35.46, 32.45, 29.53, 28.35, 22.51, 21.05, 20.01; ESIMS: m/z 486 ([M+H]⁺).

Example 1 Step 5b: Preparation of (2S,6R,7R,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxy-6-(4-methoxybenzyl)-7-(triisopropylsilyl)oxy)nonanoic acid

A high pressure reactor was charged with Pd/C (212 mg, 0.199 mmol) and a solution of (2S,6R,7R,8S)-benzyl-2-((tert-butoxycarbonyl)amino)-8-hydroxy-6-(4-methoxybenzyl)-7-((triisopropylsilyl)oxy)nonanoate (2.02 g, 3.01 mmol) in THF (10 mL). The flask was pressurized to 500 psi and stirred for 2 days (d). The reaction mixture was filtered through a pad of Celite® and concentrated to give the title compound as a sticky semi solid (1.730 g, 99%): IR (neat) 3337, 2941, 2865, 1714, 1511, 1462, 1245, 1165 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.13-6.90 (m, 2H), 6.88-6.67 (m, 2H), 4.87 (d, J=8.0 Hz, 1H), 4.22 (s, 1H), 3.96 (qd, J=6.4, 4.0 Hz, 1H), 3.79 (s, 3H), 3.76-3.62 (m, 1H), 2.93 (dd, J=14.0, 5.9 Hz, 1H), 2.44 (dd, J=13.9, 8.7 Hz, 1H), 1.92-1.65 (m, 2H), 1.62-1.48 (m, 2H), 1.44 (s, 9H), 1.34-1.14 (m, 6H), 1.14-0.71 (m, 21H); ¹³C NMR (101 MHz, CDCl₃) δ 175.71, 157.74, 155.72, 133.62, 130.02, 113.74, 70.38, 60.42, 55.27, 53.21, 43.79, 35.95, 32.41, 29.79, 28.30, 23.72, 19.11, 18.28, 14.20, 13.03; HRMS-ESI (m/z) ([M]⁺) calcd for C₃₁H₅₅NO₇Si, 581.3748. found, 581.3744.

Example 1 Step 5b: Preparation of (2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-hydroxy-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoic acid

(2S,6R)-2-((tert-Butoxycarbonyl)amino)-6-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoic acid (8.55 g, 13.1 mmol) was dissolved in THF (40 ml) in a high pressure reactor with a stir bar. To the resulting solution was added 5% Pd/C (1.40 g, 0.656 mmol) was added, the reactor was sealed and purged with H₂ (4×), and then charged to 600 psi with H₂ at room temperature. The reactor was heated to 50° C. for 12 h and then stirred at room temperature overnight. The reaction mixture was filtered through a pad of Celite® and concentrated to yield the title compound as a colorless oil contaminated with 20% p-methoxytoluene (7.76 g, 89: ¹H NMR (400 MHz, CDCl₃) δ 5.05-4.92 (m, 1H), 4.37-4.22 (m, 1H), 3.89 (qd, J=6.4, 3.5 Hz, 1H), 3.83-3.78 (m, 1H), 1.93-1.77 (m, 2H), 1.74-1.45 (m, 5H), 1.45 (s, 9H), 1.45-1.19 (m, 2H), 1.19 (d, J=5.1 Hz, 3H), 1.14-1.02 (m, 24H), 0.87 (d, J=6.6 Hz, 6H); ESIMS m/z 554.5 ([M+Na]⁺).

Example 1 Step 5c: Preparation of (2S,6R,7R,8S)-7-(benzyloxy)-2-((tert-butoxy-carbonyl)amino)-6-(2,4-difluorobenzyl)-8-hydroxynonanoic acid

A 250 mL round bottom flask was charged with (2S,6R,7R,8S)-benzyl 7-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-6-(2,4-difluorobenzyl)-8-hydroxynonanoate (2.10 g, 3.43 mmol), THF (24 mL) and H₂O (6 mL). LiOH.H₂O (153 mg, 3.64 mmol) was added, and the resulting mixture was allowed to stir at room temperature. After stirring for 2.5 h, the reaction mixture was heated to 50° C. and was stirred for an additional 17 h at that temperature. Additional portions of water (3 mL) and LiOH.H₂O (152 mg, 3.62 mmol) were added and the reaction was stirred at room temperature for 4.5 h. The reaction mixture was diluted with 1.0 M aqueous HCl (50 mL) and extracted with EtOAc (3×50 mL). The combined organic extracts were washed with saturated aqueous sodium chloride solution (NaCl, brine; 50 mL), dried over anhydrous MgSO₄, filtered, concentrated, and dried under high vacuum to obtain the title compound as a colorless oil contaminated with 10% BnOH (1.55 g, 87%): ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.26 (m, 5H), 7.15-7.05 (m, 1H), 6.82-6.69 (m, 2H), 5.03 (d, J=8.3 Hz, 1H), 4.64 (d, J=11.5 Hz, 1H), 4.55 (d, J=11.6 Hz, 1H), 4.20 (q, J=7.4 Hz, 1H), 4.03 (p, J=6.2 Hz, 1H), 3.37-3.24 (m, 1H), 2.99 (dd, J=14.0, 4.6 Hz, 1H), 2.51 (dd, J=14.0, 9.9 Hz, 1H), 2.01-1.90 (m, 1H), 1.75-1.60 (m, 1H), 1.56-1.15 (m, 17H); ¹³C NMR (101 MHz, CDCl₃) δ 176.51, 161.26 (dd, J=246.7, 12.7 Hz), 161.07 (dd, J=247.1, 12.0 Hz), 155.60, 138.35, 131.98 (dd, J=9.3, 6.9 Hz), 128.37, 127.77, 126.97, 124.00 (dd, J=15.8, 3.8 Hz), 110.83 (dd, J=20.8, 3.6 Hz), 104.38 102.95 (m), 83.36, 80.11, 73.75, 68.11, 53.17, 39.82, 32.49, 29.71, 28.85, 28.25, 22.55, 19.22; 19F NMR (376 MHz, CDCl3) δ −113.45 (d, J=7.0 Hz), −113.63 (d, J=6.7 Hz); ESIMS: m/z 522 ([M+H]⁺).

Example 1 Step 5c: Preparation of (2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoic acid

To a solution of (2S,6R)-methyl 2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoate (8.76 g, 13.2 mmol) in a mixture of THF and H₂O (125 mL/62.5 mL) was added LiOH (2.047 g, 85.0 mmol) and the resulting mixture was stirred for 24 h at 40° C. and then for another 24 h at room temperature. The reaction mixture was diluted with EtOAc and washed with 1.0 M aqueous HCl. The phases were separated and the aqueous phase was extracted with EtOAc. The combined organic phase was washed with brine, dried over MgSO₄, and concentrated to furnish the title compound as a pale yellow oil (8.55 g, 100%): IR (neat) 2943, 2866, 1715, 1513, 1392, 1247, 1162, 1038 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.26-7.20 (m, 2H), 6.88-6.82 (m, 2H), 4.96-4.83 (m, 1H), 4.51-4.31 (m, 2H), 4.31-4.20 (m, 1H), 3.88 (t, J=3.8 Hz, 1H), 3.80 (s, 3H), 3.52-3.43 (m, 1H), 1.91-1.72 (m, 2H), 1.68-1.46 (m, 5H), 1.45 (s, 9H), 1.44-1.19 (m, 2H), 1.18 (d, J=6.2 Hz, 3H), 1.18-0.98 (m, 24H), 0.86-0.80 (m, 6H); ESIMS m/z 674.6 ([M+Na]⁺).

Example 1 Step 5c: Preparation of (2S,6R,7R,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxy-7-isobutoxy-6-(2-(methylthio)ethyl)nonanoic acid

To a mixture of (2S,6R,7R,8S)-methyl 2-((tert-butoxycarbonyl)amino)-8-hydroxy-7-isobutoxy-6-(2-(methylthio)ethyl)nonanoate (326 mg, 0.725 mmol) in THF (2.4 ml) and H₂O (1.2 ml) was added LiOH.H₂O (91 mg, 2.2 mmol). The resulting mixture was stirred at room temperature for 3 h, quenched with 2N HCl (3 mL), diluted with H₂O (20 mL), and extracted with EtOAc (3×20 mL). The organic extracts were combined, dried over Na₂SO₄, filtered, and concentrated to provide the title compound as a sticky colorless oil (307 mg, 97%): ¹H NMR (400 MHz, CDCl₃) δ 5.05 (d, J=7.3 Hz, 1H), 4.31 (s, 1H), 3.88 (p, J=6.3 Hz, 1H), 3.36 (dd, J=8.5, 6.3 Hz, 1H), 3.23 (dd, J=8.6, 6.6 Hz, 1H), 3.07 (dd, J=5.7, 3.9 Hz, 1H), 2.59 (ddd, J=13.9, 8.6, 5.3 Hz, 1H), 2.48 (dt, J=12.8, 7.5 Hz, 1H), 2.10 (s, 3H), 1.84 (tt, J=13.2, 7.1 Hz, 3H), 1.78 1.62 (m, 2H), 1.55 (dd, J=13.6, 5.8 Hz, 1H), 1.46 (s, 12H), 1.22 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 2.0 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 155.81, 99.99, 84.81, 79.35, 68.26, 38.01, 32.80, 30.94, 29.22, 28.80, 28.32, 22.88, 19.51, 19.46, 19.13, 15.44; ESIMS m/z 436.3 ([M+H]⁺), 458.3 ([M+Na]⁺).

Example 1 Step 6: Preparation of tert-butyl ((3S,7R,8R,9S)-7-isopentyl-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)carbamate

A solution of (2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-hydroxy-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoic acid (7.76 g, 13.1 mmol) in anhydrous CH₂Cl₂ (500 mL) was added to a solution of MNBA (9.04 g, 26.3 mmol) and DMAP (12.8 g, 105.0 mmol) in anhydrous CH₂Cl₂ (2.5 L) at room temperature over the course of 4 h. After the addition was complete, the reaction was stirred for 12 h at room temperature, concentrated and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a sticky pale yellow solid (3.98 g, 59%): ¹H NMR (400 MHz, CDCl₃) δ 5.14 (d, J=8.2 Hz, 1H), 4.90-4.78 (m, 1H), 4.20-4.09 (m, 1H), 3.61 (t, J=7.6 Hz, 1H), 2.26-2.10 (m, 1H), 1.79-1.65 (m, 1H), 1.65-1.40 (m, 3H), 1.44 (s, 9H), 1.37 (d, J=6.5 Hz, 3H), 1.32-0.97 (m, 28H), 0.884 (d, J=6.7 Hz, 3H), 0.878 (d, J=6.7 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 173.12, 154.92, 79.62, 78.59, 75.82, 60.33, 53.07, 45.68, 36.92, 34.17, 28.64, 28.58, 28.31, 27.27, 22.82, 22.49, 18.95, 18.86, 18.38, 18.33, 13.75; ESIMS m/z 536.5 ([M+Na]⁺).

Example 2 Step 1a-1: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)(methoxymethyl)carbamate

A 4 mL vial was charged with tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)carbamate (42.0 mg, 0.074 mmol), paraformaldehyde (3.13 mg, 0.104 mmol) and CH₂Cl₂ (0.5 mL), then cooled to 0° C. under N₂. Chlorotrimethylsilane (0.026 mL, 0.201 mmol) was added to the reaction mixture, which was stirred for 45 min, then quenched by the addition of 9:1 MeOH/Et₃N (0.5 mL). The mixture was warmed to room temperature and stirred overnight. The reaction was diluted with H₂O (2 mL) and passed through a phase separator cartridge. An additional portion of CH₂Cl₂ (2 mL) was passed through the separator and the combined organics were concentrated to afford the title compound as a colorless oil: IR (neat) 3445, 2942, 2866, 1747, 1706, 1512, 1464, 1367, 1247, 1175 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.00 (d, J=8.6 Hz, 2H), 6.76 (d, J=8.6 Hz, 2H), 5.05-4.45 (m, 3H), 4.23-4.03 (m, 1H), 3.72 (s, 4H), 3.68 (t, J=8.2 Hz, 1H), 3.23 (d, J=13.1 Hz, 3H), 3.09-2.97 (m, 2H), 2.23 (td, J=12.9, 5.4 Hz, 1H), 2.01-1.96 (m, 1H), 1.73 (d, J=9.8 Hz, 1H), 1.42-1.32 (m, 3H), 1.13-1.05 (m, 21H), 0.99 (d, J=0.8 Hz, 9H), 0.91-0.77 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 155.89, 127.66, 111.86, 53.32, 45.75, 43.84, 35.14, 34.42, 26.38, 26.30, 24.77, 22.70, 17.65, 16.86, 16.56, 16.46, 15.89, 15.76, 12.07, 10.72, 10.35, 6.69, 0.00, −1.94 (Note: Peaks missing, likely due to rotamers); HRMS-ESI (m/z) ([M]⁺) calcd for C₃₃H₅₇NO₇Si, 607.3897. found, 607.3904.

Example 2 Step 1a-2: Preparation of tert-butyl ((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate

To a round bottom flask were added tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)(methoxymethyl)carbamate (1.61 g, 2.65 mmol), THF (26.5 ml) and TBAF (1.0 M, 5.30 ml, 5.30 mmol) at room temperature and an exotherm noted. The reaction was stirred at room temperature until thin layer chromatography (TLC) showed complete consumption of starting material. After approximately 2 h, the reaction was quenched by the addition of NaHCO₃ and extracted with EtOAc (3×). The combined organic extracts were washed with brine, dried over MgSO4, concentrated, and purified by column chromatography on SiO₂ (0→10%, hold, 10→20%, hold, 20→50% hold EtOAc/hexanes gradient) to furnish the title product as a colorless oil (703 mg, 59%): IR (neat) 3479, 2976, 2936, 1744, 1700, 1512, 1368, 1297, 1246, 1175 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.15-7.06 (m, 2H), 6.87-6.79 (m, 2H), 4.96-4.87 (m, 1H), 4.85-4.73 (m, 2H), 4.61-4.49 (m, 1H), 4.23-4.18 (m, 1H), 3.79 (s, 3H), 3.51 (td, J=8.8, 5.8 Hz, 1H), 3.32 (d, J=12.9 Hz, 3H), 3.01 (dd, J=13.6, 4.9 Hz, 1H), 2.44 (dd, J=16.2, 7.3 Hz, 1H), 2.07 (d, J=16.5 Hz, 1H), 1.69 (s, 2H), 1.63-1.49 (m, 3H), 1.44 (d, J=5.9 Hz, 9H), 1.40 (d, J=6.3 Hz, 3H), 0.94 (s, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.45, 158.00, 129.72, 113.97, 76.28, 55.25, 37.08, 28.24, 27.29, 19.43, 18.18 (Note: Peaks missing, likely due to rotamers); HRMS-ESI (m/z) ([M]⁺) calcd for C₂₄H₃₇NO₇, 451.2558. found, 451.257.

Example 2 Step 1b: Preparation of tert-butyl N-[(3S,7R,8R,9S)-8-benzyloxy-9-methyl-2-oxo-7-(p-tolylmethyl)oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate (F230)

A 25 mL screw top vial was charged with tert-butyl ((3S,7R,8R,9S)-8-(benzyloxy)-9-methyl-7-(4-methylbenzyl)-2-oxooxonan-3-yl)carbamate (720 mg, 1.50 mmol), DMAP (91.0 mg, 0.75 mmol), and anhydrous CH₃CN (7.5 mL). To the mixture was added di-tert-butyl dicarbonate (1.30 g, 5.98 mmol) and the reaction was stirred at room temperature for 17 h and then warmed to 50° C. and stirred for an additional 29 h. The reaction mixture was concentrated under a gentle stream of N₂ and the crude concentrate was purified by column chromatography on SiO₂ (gradient, 0→20% acetone in hexane) to give tert-butyl ((3S,7R,8R,9S)-8-(benzyloxy)-9-methyl-7-(4-methylbenzyl)-2-oxooxonan-3-yl)carbamate as a white solid (167 mg, 19%): mp 164-166° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.26 (m, 5H), 7.07 (d, J=8.1 Hz, 2H), 7.03 (d, J=8.0 Hz, 2H), 4.88-4.75 (m, 3H), 4.61 (d, J=10.8 Hz, 1H), 3.35 (t, J=9.1 Hz, 1H), 3.10 (dd, J=13.3, 3.3 Hz, 1H), 2.40-2.28 (m, 4H), 2.22 (tt, J=13.5, 7.2 Hz, 1H), 2.02-1.88 (m, 2H), 1.64-1.41 (m, 24H), 0.96-0.84 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 171.13, 152.83 (2C), 137.98, 137.51, 135.31, 129.01, 128.77, 128.54, 127.89, 127.76, 84.14, 82.64 (2C), 75.44, 75.21, 57.57, 45.77, 36.43, 30.83, 27.97 (6C), 26.84, 21.04, 19.67, 18.49; ESIMS m/z 604 ([M+Na]⁺).

Example 3 Step 1: Preparation of tert-butyl ((3S,7R,8R,9S)-8-(allyloxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate

A solution of tert-butyl ((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (350 mg, 0.775 mmol), palladium tetrakis(triphenylphosphine) (90 mg, 0.078 mmol), and allyl tert-butyl carbonate (758 mg, 4.79 mmol) in degassed THF (3876 μl) was heated to 60° C. and stirred for 4 h. The reaction mixture was cooled to room temperature and purified directly by column chromatography on SiO₂ (EtOAc/Hex gradient) to afford the title product as a light yellow oil (200 mg, 52.5%): IR (neat) 2977, 2934, 2836, 1746, 1702, 1511, 1367, 1297, 1246, 1175 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.07 (d, J=8.5 Hz, 2H), 6.81 (d, J=8.6 Hz, 2H), 6.02-5.88 (m, 1H), 5.33 (dd, J=17.2, 1.6 Hz, 1H), 5.20 (dd, J=10.4, 1.5 Hz, 1H), 4.94-4.81 (m, 2H), 4.76 (t, J=10.3 Hz, 1H), 4.60-4.50 (m, 1H), 4.28 (dd, J=11.8, 5.6 Hz, 1H), 4.22-4.15 (m, 1H), 4.09 (dd, J=11.9, 5.3 Hz, 1H), 3.78 (s, 3H), 3.30 (d, J=14.5 Hz, 3H), 3.21 (t, J=9.0 Hz, 1H), 3.03 (dd, J=13.5, 3.4 Hz, 1H), 2.34-2.22 (m, 1H), 2.15-1.98 (m, 1H), 1.80 (s, 1H), 1.65-1.59 (m, 2H), 1.50-1.39 (m, 13H), 0.90-0.76 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.53, 157.82, 134.40, 134.36, 132.63, 129.69, 117.12, 113.73, 84.28, 84.24, 81.09, 74.62, 58.57, 57.06, 55.24, 55.22, 46.01, 35.97, 28.32, 28.23, 26.57, 19.22, 18.26; HRMS-ESI (m/z) ([M]⁺) calcd for C₂₇H₄₁NO₇, 491.2883. found, 491.2862.

Example 3 Step 2a: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-propoxyoxonan-3-yl)(methoxymethyl)carbamate (F221)

A vial was charged with 5 wt % Pd/C (26.0 mg, 0.012 mmol) and a solution of tert-butyl ((3S,7R,8R,9S)-8-(allyloxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (200 mg, 0.407 mmol) in EtOAc (1 mL). The vial was evacuated and backfilled with H₂ (3×) and then stirred vigorously under one atmosphere of H₂ (balloon) at room temperature for 15 h. The reaction mixture was filtered through a plug of Celite® and concentrated to the title compound as a colorless oil (168 mg, 84%) IR (neat) 3368, 2973, 2936, 2877, 1746, 1705, 1511, 1454, 1367, 1175 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.12-7.03 (m, 2H), 6.87-6.77 (m, 2H), 5.04-4.67 (m, 2H), 4.21-4.09 (m, 1H), 3.78 (s, 3H), 3.71 (dtd, J=8.6, 6.8, 1.9 Hz, 1H), 3.50 (dtd, J=8.4, 6.6, 1.7 Hz, 1H), 3.34-3.25 (m, 3H), 3.12 (td, J=9.3, 3.6 Hz, 1H), 3.07-2.98 (m, 1H), 2.27 (ddd, J=13.4, 11.7, 6.2 Hz, 1H), 2.07 (s, 2H), 1.76 (s, 1H), 1.71-1.54 (m, 4H), 1.55-1.33 (m, 14H), 0.97 (td, J=7.4, 1.0 Hz, 3H), 0.81 (s, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.30, 157.80, 132.75, 129.69, 113.73, 99.98, 84.02, 83.99, 81.11, 75.59, 75.52, 55.25, 55.23, 46.20, 35.86, 35.82, 28.32, 26.56, 23.59, 19.21, 18.19, 18.12, 10.75; HRMS-ESI (m/z) ([M]⁺) calcd for C₂₇H₄₃NO₇, 493.3040. found, 493.3018.

Example 3 Step 2b-1: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(4-fluorobenzyl)-9-methyl-2-oxo-8-(2-oxoethoxy)oxonan-3-yl)(methoxymethyl)carbamate

A mixture of tert-butyl ((3S,7R,8R,9S)-8-(allyloxy)-7-(4-fluorobenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (480 mg, 1.001 mmol), NaHCO₃ (8.41 mg, 0.10 mmol) and anhydrous MeOH (0.31 mL) in anhydrous CH₂Cl₂ (9.7 mL) was treated with ozone at −78° C. until the solution became light blue in color. The mixture was purged with nitrogen until colorless and then quenched by addition of dimethyl sulfide (0.148 mL, 2.00 mmol). The reaction mixture was warmed to room temperature and stirred for 20 h, concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/EtOAc) to provide the title compound as a mixture of rotamers in the form of a white solid (461 mg, 96%): mp 51-53° C.; IR (neat) 2935, 1740, 1701, 1509, 1367, 1297, 1173, 1081 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 9.68 (s, 1H), 7.17-7.06 (m, 2H), 7.00-6.91 (m, 2H), 4.99-4.16 (m, 6H), 3.87-2.97 (m, 4H), 2.46-2.27 (m, 1H), 2.17-2.01 (m, 1H), 1.97-1.75 (m, 1H), 1.74-1.37 (m, 17H), 0.95-0.78 (m, 1H); HRMS-ESI (m/z) ([M]⁺) calcd for C₂₅H₃₆FNO₇, 481.2476. found, 481.2481.

Example 3 Step 2b-2: Preparation of tert-butyl ((3S,7R,8R,9S)-8-(2,2-difluoro-ethoxy)-7-(4-fluorobenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (F212)

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(4-fluorobenzyl)-9-methyl-2-oxo-8-(2-oxoethoxy)oxonan-3-yl)(methoxymethyl)carbamate (461 mg, 0.957 mmol) in anhydrous CH₂Cl₂ (6.0 mL) at 0° C. was added a ˜50% toluene solution of Deoxo-Fluor® (0.710 mL, 1.92 mmol) in anhydrous CH₂Cl₂ (4 mL) dropwise at 0° C. and the reaction mixture was stirred at 0° C. for 1 h. The reaction mixture was concentrated and purified by column chromatography on SiO₂ (gradient, hexanes/EtOAc) to provide the title compound as a mixture of rotamers in the form of a white solid (399 mg, 83%): IR (neat) 2978, 2938, 1747, 1700, 1509, 1368, 1297, 1080 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.16-7.04 (m, 2H), 7.02-6.89 (m, 2H), 5.86 (tt, J=55.1, 4.0 Hz, 1H), 4.95-4.71 (m, 3H), 4.60-4.46 (m, 0.5H), 4.25-4.13 (m, 0.5H), 4.04-3.89 (m, 1H), 3.84-3.69 (m, 1H), 3.37-3.18 (m, 3H), 3.03 (dd, J=13.3, 3.5 Hz, 1H), 2.41-2.30 (m, 1H), 2.19-1.99 (m, 1H), 1.88-1.75 (m, 1H), 1.72-1.32 (m, 17H), 0.93-0.75 (m, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ −117.16, −117.27, −125.28-−125.61 (m, 2F); HRMS-ESI (m/z) ([M]⁺) calcd for C₂₅H₃₆F₃NO₆, 503.2495. found, 503.2499.

Example 4 Step 1: tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((3-oxobut-1-en-1-yl)oxy)oxonan-3-yl)(methoxymethyl)carbamate

A round bottomed flask was charged with tert-butyl ((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (400 mg, 0.886 mmol) in CH₂Cl₂ (4429 μl). To the solution was added DABCO (4.97 mg, 0.044 mmol) and the reaction mixture was cooled to 0° C. under N₂. Upon addition of but-3-yn-2-one (83 μl, 1.063 mmol), the colorless solution became dark brown-orange. After stirring for 2 h, the reaction mixture was concentrated and purified directly by column chromatography on SiO₂ (0→10%, hold, 10→20%, hold, 20→50% hold EtOAc/hexanes gradient) to afford the title compound as a thick colorless oil (257 mg, 55.8%): ¹H NMR (400 MHz, CDCl₃) δ 7.43 (d, J=12.2 Hz, 1H), 7.03 (d, J=8.6 Hz, 2H), 6.81 (d, J=8.6 Hz, 2H), 5.75 (d, J=12.4 Hz, 1H), 5.06-4.85 (m, 2H), 4.82-4.73 (m, 1H), 4.61-4.50 (m, 1H), 4.26-4.14 (m, 1H), 3.78 (s, 3H), 3.37-3.26 (m, 3H), 2.82 (dd, J=13.6, 4.0 Hz, 1H), 2.41-2.28 (m, 1H), 2.24-2.01 (m, 1H), 2.18 (s, 3H), 1.62-1.39 (m, 12H), 1.34 (d, J=6.4 Hz, 3H), 1.26 (t, J=7.1 Hz, 2H), 0.92 (dt, J=13.6, 4.6 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 197.24, 173.18, 163.24, 158.03, 155.34, 131.19, 129.61, 113.83, 108.08, 88.73, 88.61, 81.19, 76.86, 76.23, 75.39, 72.61, 72.49, 58.42, 56.97, 55.41, 55.14, 44.87, 35.82, 30.38, 29.45, 28.43, 28.27, 28.16, 26.38, 26.18, 19.16, 18.24; ESIMS m/z 542.4 ([M+Na)]⁺).

Example 4 Step 2: Preparation of ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl)(methoxymethyl)carbamate

A round bottomed flask was charged with tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((3-oxobut-1-en-1-yl)oxy)oxonan-3-yl)(methoxymethyl)-carbamate (257 mg, 0.495 mmol), 5 wt % Pd/C (35 mg, 0.033 mmol) and EtOAc (4 mL). The reaction flask was briefly evacuated under vacuum and backfilled with H₂ (3×) and then stirred vigorously under an H₂ atmosphere at room temperature overnight. The reaction mixture was filtered through a plug of Celite® and concentrated to afford the title compound as a colorless oil (256 mg, 99%): ¹H NMR (400 MHz, CDCl₃) δ 7.14-7.01 (m, 2H), 6.87-6.77 (m, 2H), 4.94-4.73 (m, 3H), 4.08-3.95 (m, 1H), 3.88-3.71 (m, 1H), 3.78 (s, 3H), 3.39-3.25 (m, 3H), 3.21-3.09 (m, 1H), 3.07-2.88 (m, 1H), 2.70 (t, J=6.2 Hz, 1H), 2.37-2.22 (m, 1H), 2.20 (s, 2H), 1.80-1.59 (m, 3H), 1.58-1.35 (m, 16H), 1.32-1.17 (m, 2H), 0.86-0.71 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 206.65, 173.53, 157.82, 132.63, 129.72, 129.68, 113.81, 113.74, 84.56, 68.21, 55.23, 45.95, 43.90, 35.95, 30.73, 28.31, 28.21, 21.05, 19.42, 19.26, 18.17; ESIMS m/z 544.3 ([M+Na]⁺).

Example 4 Step 3: Preparation of tert-butyl ((3S,7R,8R,9S)-8-(3,3-difluorobutoxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (F218)

A 20 mL vial was charged with tert-butyl ((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl)(methoxymethyl)carbamate (250 mg, 0.479 mmol), CH₂Cl₂ (3 mL) and Deoxo-Fluor® (1.04 g, 2.35 mmol) and the mixture was stirred vigorously at room temperature under N₂ for 12 h. An additional portion of Deoxo-Fluor® (900 mg, 4.07 mmol) was added and reaction was stirred for an additional 48 h. Upon complete consumption of starting material, the reaction mixture was quenched (carefully!) with saturated aqueous NaHCO₃ solution and extracted with CH₂Cl₂ (3×). The mixture was passed through a phase separator and the organic phase was concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/EtOAc) to provide the title compound as a colorless oil (106.6 mg, 40.9%): ¹H NMR (400 MHz, CDCl₃) d 7.10-7.00 (m, 2H), 6.88-6.76 (m, 2H), 4.97-4.82 (m, 2H), 4.81-4.71 (m, 1H), 4.55 (s, 1H), 4.19 (t, J=9.6 Hz, 1H), 3.97-3.84 (m, 1H), 3.78 (s, 3H), 3.72 (dt, J=9.1, 6.8 Hz, 1H), 3.37-3.26 (m, 3H), 3.14 (td, J=8.9, 3.2 Hz, 1H), 2.97 (dd, J=13.4, 3.5 Hz, 1H), 2.37-2.24 (m, 1H), 2.26-2.02 (m, 3H), 1.81-1.57 (m, 5H), 1.58-1.23 (m, 14H), 0.89-0.77 (m, 1H); ¹⁹F NMR (376 MHz, CDCl₃) d −89.52, −89.56 (d, J=72.5 Hz); ESIMS m/z 566.3 ([M+Na]⁺).

Example 5 Preparation of (2S,3R,4R,8S)-8-((tert-butoxycarbonyl)-(methoxymethyl)-amino)-4-(4-methoxybenzyl)-2-methyl-9-oxooxonan-3-yl cyclopentanecarboxylate (F217)

A 20 mL vial was charged with tert-butyl ((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (200 mg, 0.443 mmol), CH₂Cl₂ (2215 μl), NEt₃ (185 μl, 1.329 mmol) and DMAP (5.41 mg, 0.044 mmol). The reaction mixture was cooled to 0° C. in an ice bath under N₂ and cyclopentanecarbonyl chloride (76 mg, 0.576 mmol) was added in one portion. The reaction became dark brownish-yellow. After stirring for 2 h, the reaction mixture was quenched by the addition of saturated aqueous NaHCO₃. The mixture was extracted with CH₂Cl₂ (3×) and the combined organic layers were washed with brine, dried over MgSO4, concentrated, and purified by column chromatography on SiO₂ (0→100% EtAOx/hexanes) to provide the title compound as a yellow solid (85 mg, 35.0%): ¹H NMR (400 MHz, CDCl₃) δ 7.01 (d, J=8.5 Hz, 4H), 6.81 (d, J=8.4 Hz, 4H), 5.06-4.85 (m, 3H), 4.77 (d, J=11.6 Hz, 1H), 4.57 (dd, J=10.7, 6.0 Hz, 0H), 4.29-4.17 (m, 1H), 3.78 (s, 3H), 3.38-3.26 (m, 3H), 2.74 (p, J=8.0 Hz, 1H), 2.61 (dd, J=13.7, 3.7 Hz, 1H), 2.31 (dd, J=13.7, 11.1 Hz, 1H), 2.20-2.07 (m, 1H), 1.99-1.52 (m, 8H), 1.51-1.40 (m, 9H), 1.27 (d, J=5.8 Hz, 3H), 1.15-0.96 (m, 1H), 0.97-0.87 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 176.26, 173.56, 157.94, 155.49, 131.94, 129.59, 113.80, 81.21, 75.54, 72.72, 58.52, 55.43, 55.22, 44.32, 44.04, 35.77, 30.09, 30.00, 29.58, 28.20, 26.48, 25.72, 25.70, 19.09, 17.56; ESIMS m/z 570.5 ([M+Na]⁺).

Example 6 Preparation of tert-butyl ((3S,7R,8R,9S)-7-isopentyl-8-methoxy-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (F205)

To an oven-dried vial were added N1,N1,N8,N8-tetramethylnaphthalene-1,8-diamine (Proton Sponge®; 1.63 g, 7.60 mmol), tert-butyl ((3S,7R,8R,9S)-8-hydroxy-7-isopentyl-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (436 mg, 1.086 mmol), anhydrous Na₂SO₄ (1.15 g, 8.10 mmol), and trimethyloxonium tetrafluoroborate (723 mg, 4.89 mmol) in anhydrous CH₂Cl₂ (11 mL) at 0° C. The reaction mixture was slowly warmed to room temperature and stirred for 5 h. The reaction mixture was diluted with EtOAc, filtered, and the filtrate was washed with water. The phases were separated and the aqueous phase was extracted with additional EtOAc, and the combined organic phases were washed with 1.0 M aqueous sodium bisulfate (NaHSO₄), washed with saturated aqueous NaHCO₃, dried over MgSO₄, concentrated, and purified by column chromatography on SiO₂ (gradient, hexanes/EtOAc) to provide the title compound as a mixture of rotamers in the form of a white solid (320 mg, 71%): IR (neat) 2934, 1747, 1705, 1454, 1366, 1296, 1170, 1080 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 4.97-4.70 (m, 3H), 4.60-4.47 (m, 0.5H), 4.25-4.11 (m, 0.5H), 3.49 (s, 3H), 3.40-3.28 (m, 3H), 2.97-2.86 (m, 1H), 2.17-2.01 (m, 1H), 1.79-1.42 (m, 16H), 1.42 (d, J=6.4 Hz, 3H), 1.31-1.07 (m, 3H), 0.99-0.82 (m, 7H); ¹³C NMR (101 MHz, CDCl₃) δ 173.54, 155.56, 155.39, 86.39, 81.02, 80.98, 76.34, 75.50, 74.70, 74.43, 61.04, 58.62, 57.11, 55.45, 55.36, 43.42, 36.40, 30.67, 29.62, 28.20, 28.15, 28.09, 27.31, 27.04, 23.05, 22.12, 19.19, 18.10; HRMS-ESI (m/z) ([M]⁺) calcd for C₂₂H₄₁NO₆, 415.2934. found, 415.2943.

Example 7 Step 1: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-((tert-butyldimethylsilyl)-oxy)ethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (3.01 g, 5.77 mmol) in anhydrous THF (58 mL) was added a 1M solution of TBAF in THF (8.65 ml, 8.65 mmol). The resulting yellow solution was stirred at room temperature for 4 h, poured into 100 mL ½ saturated NaCl solution, and extracted with EtOAc (3×50 mL). The organic extracts were combined, dried over MgSO₄, filtered, and concentrated to provide a light yellow oil, which was purified by column chromatography on SiO₂ (5→25% acetone/hexanes) to provide the title compound as a hard white foam (1.95 g, 83%): ¹H NMR (400 MHz, CDCl₃) δ 7.44-7.17 (m, 2H), 6.95 (t, J=8.2 Hz, 3H), 5.17-4.98 (m, 2H), 4.29-4.11 (m, 2H), 3.75-3.53 (m, 2H), 2.28 (dt, J=13.4, 6.7 Hz, 1H), 2.03-1.88 (m, 1H), 1.88-1.74 (m, 2H), 1.74-1.62 (m, 1H), 1.62-1.48 (m, 2H), 1.44 (s, 10H), 1.28 (d, J=6.5 Hz, 3H), 1.26-1.19 (m, 1H), 1.14 (ddd, J=15.1, 7.5, 3.6 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.30, 159.23, 154.90, 129.69, 121.20, 115.33, 80.99, 79.92, 74.68, 60.96, 52.99, 39.55, 34.07, 28.56, 28.33, 19.13, 18.36; ESIMS m/z 408.3 ([M+H]⁺), 430.3 ([M+Na]⁺).

Example 7 Step 2a: Preparation of tert-butyl ((3S,7R,8R,9S)-9-methyl-2-oxo-8-phenoxy-7-(2-phenoxyethyl)oxonan-3-yl)carbamate (F240)

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (215 mg, 0.528 mmol) in anhydrous toluene (5.3 mL) were added Ph₃Bi(OAc)₂ (354 mg, 0.633 mmol), diacetoxycopper (19.17 mg, 0.106 mmol), and N-cyclohexyl-N-methylcyclohexanamine (224 μl, 1.055 mmol). The resulting mixture was heated to 50° C. for 20 h, cooled to room temperature, filtered through a plug of Celite®, and rinsed the plug with toluene. The filtrate was concentrated and purified by column chromatography on SiO₂ (2→20% acetone/hexanes) to provide the title compound as a sticky oil (253 mg). ¹H NMR gives the desired product, but it is contaminated with Cy₂NMe. The oil was dissolved in CH₂Cl₂ (25 mL) and the solution was washed with 0.2 M HCl (25 mL), dried over Na₂SO₄, decanted, and concentrated to provide 234 mg of the desired product as a hard white foam. The product was repurified by column chromatography on SiO₂ (5→20% acetone/hexanes) to provide the title compound as a hard white foam (199 mg, 78%): ¹H NMR (400 MHz, CDCl₃) δ 7.33-7.20 (m, 4H), 6.93 (p, J=7.4 Hz, 4H), 6.86-6.75 (m, 2H), 5.21-4.97 (m, 2H), 4.32-4.11 (m, 2H), 3.94 (t, J=6.6 Hz, 2H), 2.34-2.22 (m, 1H), 2.06 (dd, J=16.4, 4.9 Hz, 2H), 1.93 (d, J=12.6 Hz, 1H), 1.89-1.78 (m, 1H), 1.78-1.65 (m, 2H), 1.44 (s, 9H), 1.31 (d, J=6.5 Hz, 3H), 1.19 (dd, J=25.8, 13.7 Hz, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.28, 159.34, 158.76, 154.89, 129.68, 129.39, 121.17, 120.61, 115.40, 114.42, 99.98, 81.14, 79.92, 74.68, 66.01, 53.01, 40.14, 34.11, 30.49, 19.20, 18.35; ESIMS m/z 484.3 ([M+H]⁺).

Example 7 Step 2b: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(2-methoxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (F242)

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (400 mg, 0.982 mmol) and Proton Sponge® (841 mg, 3.93 mmol) in anhydrous CH₂Cl₂ (10 mL) at 0° C. (icewater bath) was added trimethyloxonium tetrafluoroborate (290 mg, 1.963 mmol; weighed under N₂), and the resulting mixture was stirred at 0° C. for 3 h, quenched with 1N HCl (20 mL), and extracted with CH₂Cl₂ (3×20 mL). The organic extracts were combined, dried over Na₂SO₄, filtered, and concentrated to provide an oily white solid, which was purified by column chromatography on SiO₂ (5→20% acetone/hexanes) to provide the title compound as a white, crystalline solid (321 mg, 78%): ¹H NMR (400 MHz, CDCl₃) δ 7.27 (t, J=8.0 Hz, 2H), 6.94 (dd, J=7.7, 3.3 Hz, 3H), 5.10 (d, J=8.1 Hz, 1H), 5.08-4.98 (m, 1H), 4.20 (q, J=7.9, 6.9 Hz, 2H), 3.36 (t, J=6.5 Hz, 2H), 3.25 (s, 3H), 2.27 (dt, J=13.3, 6.8 Hz, 1H), 1.88 (ddt, J=10.8, 6.9, 3.9 Hz, 2H), 1.83-1.71 (m, 1H), 1.70-1.61 (m, 1H), 1.60-1.52 (m, 1H), 1.44 (s, 10H), 1.28 (d, J=6.5 Hz, 3H), 1.25-1.16 (m, 1H), 1.16-1.05 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.28, 159.46, 154.90, 129.61, 121.05, 115.38, 81.12, 79.86, 74.71, 70.79, 58.42, 52.99, 40.09, 34.12, 30.53, 28.33, 28.15, 19.07, 18.36; ESIMS m/z 422.3 ([M+H]⁺), 444.3 ([M+Na]⁺).

Example 7 Step 2c-1: Preparation of tert-butyl ((3S,7R,8R,9S)-9-methyl-2-oxo-7-(2-oxoethyl)-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (250 mg, 0.613 mmol) in CH₂Cl₂ (6.1 mL) at 0° C. was added Dess-Martin periodinane (286 mg, 0.675 mmol). The resulting mixture was stirred at 0° C. for 2 h, quenched with sat. aqueous sodium thiosulfate (Na₂S₂O₃; 3 mL) and sat. aqueous NaHCO₃ (3 mL) solution, and then removed from the cold bath and stirred vigorously for 10 min. The phases were separated and the aqueous phase was extracted with CH₂Cl₂ (2×6 mL) and the combined organic extracts were dried over Na₂SO₄, filtered, and concentrated to provide the title compound as a fluffy white foam (255.4 mg, 98%): ¹H NMR (400 MHz, CDCl₃) δ 9.65 (t, J=1.7 Hz, 1H), 7.29 (dd, J=8.7, 7.4 Hz, 2H), 7.02-6.93 (m, 1H), 6.88 (d, J=7.9 Hz, 2H), 5.23-5.08 (m, 2H), 4.30-4.10 (m, 2H), 2.60 (dd, J=16.0, 5.4 Hz, 1H), 2.44 (d, J=6.4 Hz, 1H), 2.38-2.21 (m, 2H), 1.73 (ddd, J=19.5, 13.8, 9.2 Hz, 3H), 1.44 (s, 9H), 1.37-1.22 (m, 5H); ¹³C NMR (101 MHz, CDCl₃) δ 200.78, 173.29, 158.65, 154.90, 129.80, 129.73, 121.59, 115.23, 80.63, 79.98, 74.23, 53.28, 46.09, 36.71, 33.64, 31.78, 28.33, 19.72, 18.18; ESIMS m/z 428.2 ([M+Na]⁺).

Example 7 Step 2c-2: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(2,2-difluoroethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl ((3S,7R,8R,9S)-9-methyl-2-oxo-7-(2-oxoethyl)-8-phenoxyoxonan-3-yl)carbamate (241 mg, 0.594 mmol) in anhydrous CH₂Cl₂ (6 mL) at 0° C. (icewater bath) was added Deoxo-Fluor® (230 μl, 1.248 mmol). The reaction was stirred for 2.5 h, concentrated, and purified by column chromatography on SiO₂ (2→20% acetone/hexanes) to provide the title compound as a white crystalline solid (153.2 mg, 60.3%): ¹H NMR (400 MHz, CDCl₃) δ 7.29 (dtd, J=10.1, 4.8, 2.5 Hz, 2H), 7.01-6.95 (m, 1H), 6.93 (d, J=8.0 Hz, 2H), 5.83 (tt, J=57.0, 4.6 Hz, 1H), 5.18-5.00 (m, 2H), 4.21 (q, J=8.7 Hz, 2H), 2.29 (dt, J=13.4, 6.8 Hz, 1H), 2.12-1.94 (m, 2H), 1.91-1.77 (m, 2H), 1.77-1.70 (m, 1H), 1.66-1.54 (m, 1H), 1.44 (s, 9H), 1.30 (d, J=6.5 Hz, 3H), 1.27-1.16 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.21, 158.93, 154.89, 129.83, 121.55, 116.74 (t, J=239.4 Hz), 115.25, 80.57, 79.97, 74.39, 53.02, 37.53, 35.74 (t, J=21.1 Hz), 33.86, 29.44, 28.32, 19.21, 18.27; ESIMS m/z 450.3 ([M+Na)⁺]).

Example 7 Step 2d-1: Preparation of tert-butyl ((3S,7R,8R,9S)-7-(2-bromoethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (F249)

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (700 mg, 1.718 mmol) in CH₂Cl₂ (17 mL) at 0° C. (icewater bath) were added perbromomethane (627 mg, 1.890 mmol) and triphenylphosphine (541 mg, 2.061 mmol). After 70 min, TLC (2:1 hexanes:acetone) showed incomplete conversion so additional CBr₄ and Ph₃P (64 mg and 54 mg, respectively) were added and the reaction was stirred for an additional 20 min. The reaction was concentrated and purified by column chromatography on SiO₂ (5→20% acetone/hexanes) to provide the title compound as a hard white foam (712 mg, 88%): ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.27 (m, 2H), 7.03-6.82 (m, 3H), 5.18-4.99 (m, 2H), 4.21 (q, J=8.7 Hz, 2H), 3.44 (ddd, J=10.0, 7.4, 5.0 Hz, 1H), 3.33 (ddd, J=9.9, 8.4, 6.9 Hz, 1H), 2.28 (dt, J=13.0, 6.6 Hz, 1H), 2.10 (dtd, J=12.6, 7.9, 4.5 Hz, 1H), 2.05-1.96 (m, 1H), 1.85-1.73 (m, 2H), 1.73-1.61 (m, 1H), 1.44 (s, 10H), 1.30 (d, J=6.5 Hz, 3H), 1.28-1.20 (m, 1H), 1.20-1.09 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.20, 159.18, 154.89, 129.74, 121.33, 115.37, 80.94, 79.95, 74.57, 53.02, 41.18, 34.13, 33.95, 31.54, 28.33, 19.13, 18.29; HRMS-ESI (m/z) ([M+Na]⁺) calcd for C₂₂H₃₂BrNNaO₅, 492.1356. found, 492.1352.

Example 7 Step 2d-2: Preparation of tert-butyl ((3S,7S,8R,9S)-7-ethyl-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (F250)

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-bromoethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (408 mg, 0.867 mmol) and AIBN (14.24 mg, 0.087 mmol) in anhydrous toluene (8.7 mL) was added Bu₃SnH (257 μl, 0.954 mmol), and the reaction was heated to 80° C. After 1 h, TLC (4:1 hexanes:acetone) still showed starting material. An additional 0.5 equivalents of Bu₃SnH and 0.05 equiv AIBN were added and the reaction was stirred for an additional 1 h at 80° C. The reaction was cooled to room temperature, stirred with 10% aqueous potassium fluoride (KF) solution (7 mL) for 20 h, and partitioned between Et₂O (20 mL) and sat. NaCl solution (20 mL). The phases were separated and the aqueous phase was extracted with Et₂O (2×20 mL). The organic extracts were combined, dried over MgSO₄, filtered and concentrated to provide a white solid, which was purified by column chromatography on SiO₂ (5→20% acetone/hexanes) to provide the title compound as a white solid (295 mg, 87%): ¹H NMR (400 MHz, CDCl₃) δ 7.38-7.16 (m, 2H), 7.00-6.87 (m, 3H), 5.19-4.97 (m, 2H), 4.18 (t, J=8.8 Hz, 2H), 2.27 (dt, J=13.1, 6.7 Hz, 1H), 1.91-1.77 (m, 1H), 1.70-1.58 (m, 3H), 1.58-1.48 (m, 1H), 1.44 (s, 9H), 1.28 (d, J=6.5 Hz, 3H), 1.25-1.14 (m, 2H), 1.12-1.01 (m, 1H), 0.86 (t, J=7.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 173.34, 159.68, 154.91, 129.58, 120.95, 115.40, 81.44, 79.86, 74.74, 53.00, 44.96, 34.20, 28.34, 27.85, 27.03, 26.85, 23.50, 18.74, 18.40, 17.53, 13.61, 11.86; ESIMS m/z 392.3 ([M+H]⁺), 414.3 ([M+Na]⁺).

Example 7 Step 2e: Preparation of ((3S,7R,8R,9S)-7-(2-fluoroethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)carbamate (F235)

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)carbamate (200 mg, 0.516 mmol) in anhydrous chloroform (CHCl₃; 5.1 mL) at 0° C. (icewater bath) was added Deoxo-Fluor® (114 μl, 0.619 mmol). The resulting solution was stirred at 0° C. for 4 h, poured into H₂O (20 mL) and extracted with CH₂Cl₂ (3×20 mL). The organic extracts were combined, dried over Na₂SO₄, filtered, and concentrated to provide a yellow solid, which was purified by column chromatography on SiO₂ (2→25% acetone/hexanes) to provide the title compound as a white solid (177 mg, 88%) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 5.07 (d, J=8.1 Hz, 1H), 4.92-4.78 (m, 1H), 4.55 (td, J=5.6, 3.2 Hz, 1H), 4.47-4.37 (m, 1H), 4.15 (dt, J=10.7, 7.8 Hz, 1H), 3.43 (dd, J=8.4, 6.6 Hz, 1H), 3.24 (dd, J=8.4, 6.4 Hz, 1H), 3.09-2.96 (m, 1H), 2.22 (dt, J=13.4, 6.7 Hz, 1H), 2.10-1.95 (m, 1H), 1.83 (dp, J=13.2, 6.6 Hz, 1H), 1.67 (d, J=7.9 Hz, 3H), 1.64-1.53 (m, 2H), 1.44 (s, 9H), 1.40 (d, J=6.4 Hz, 3H), 1.17 (q, J=11.6 Hz, 1H), 1.08-0.97 (m, 1H), 0.94-0.88 (m, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 173.30, 154.91, 83.83, 83.78, 82.14, 80.21, 79.82, 75.14, 52.97, 39.75, 34.06, 31.57, 31.37, 29.15, 28.69, 28.32, 19.44, 19.40, 19.07, 18.14; ESIMS m/z 412.3 ([M+Na]⁺).

Example 7 Step 2f-1: Preparation of tert-butyl ((3S,7R,8R,9S)-9-methyl-7-(2-((2-nitrophenyl)selanyl)ethyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl ((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (227 mg, 0.557 mmol) in anhydrous THF (5.6 mL) at 0° C. (ice water bath) were added 1-nitro-2-selenocyanatobenzene (177 mg, 0.780 mmol) and tributylphosphine (223 μl, 0.891 mmol). The resulting solution was stirred for 3 h and then treated with additional 1-nitro-2-selenocyanatobenzene and tributylphospine (53 mg and 67 μL, respectively). The reaction was stirred for an additional 1 h, then poured into 20 mL sat. NaCl solution and extracted with 3×20 mL EtOAc. The organic extracts were combined, dried over MgSO₄, filtered, and concentrated to provide a brown oil, which was purified by column chromatography on SiO₂ (2→20% acetone/hexanes) to provide the title compound as a bright yellow solid (294 mg, 89%): ¹H NMR (400 MHz, CDCl₃) δ 8.24 (dt, J=8.2, 1.0 Hz, 1H), 7.36-7.19 (m, 5H), 7.00-6.92 (m, 1H), 6.92-6.84 (m, 2H), 5.16-4.98 (m, 2H), 4.21 (t, J=8.5 Hz, 2H), 3.05-2.76 (m, 2H), 2.30 (dt, J=13.2, 6.7 Hz, 1H), 1.94 (tdq, J=28.6, 14.1, 8.4, 6.4 Hz, 3H), 1.78-1.64 (m, 2H), 1.60 (d, J=4.5 Hz, 1H), 1.45 (s, 9H), 1.30 (d, J=6.5 Hz, 3H), 1.27-1.13 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.23, 159.12, 154.89, 146.86, 133.45, 133.21, 129.76, 128.95, 126.41, 125.29, 121.34, 115.33, 80.99, 79.97, 74.59, 52.99, 43.60, 34.00, 29.99, 28.58, 28.33, 24.24, 19.15, 18.29; ESIMS m/z 593.2 ([M+Na]⁺).

Example 7 Step 2f-2: Preparation of tert-butyl ((3S,7R,8R,9S)-9-methyl-2-oxo-8-phenoxy-7-vinyloxonan-3-yl)carbamate (F259)

To a solution of tert-butyl ((3S,7R,8R,9S)-9-methyl-7-(2-((2-nitrophenyl)-selanyl)ethyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamate (284 mg, 0.480 mmol) in THF (4.8 mL) was added 30% aqueous hydrogen peroxide (H₂O₂ 392 μl, 3.84 mmol), and the resulting bright yellow solution was stirred at room temperature for 3 d. The reaction was cooled to 0° C. (icewater bath), quenched with sat. aqueous NaHSO₃ solution (4 mL), diluted with H₂O (20 mL), and extracted with EtOAc (3×20 mL). The organic extracts were combined, dried over MgSO₄, filtered, and concentrated to the title compound as an orange solid (134.9 mg, 72%): ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.19 (m, 2H), 7.02-6.86 (m, 3H), 5.76 (ddd, J=17.2, 10.3, 8.0 Hz, 1H), 5.17-5.06 (m, 2H), 5.03 (d, J=17.1 Hz, 1H), 4.94 (d, J=10.4 Hz, 1H), 4.28 (t, J=8.8 Hz, 1H), 4.25-4.17 (m, 1H), 2.56-2.41 (m, 1H), 2.27 (dt, J=13.5, 6.6 Hz, 1H), 1.85 (td, J=14.6, 7.1 Hz, 1H), 1.75 (dt, J=14.8, 7.3 Hz, 1H), 1.65 (s, 1H), 1.44 (s, 9H), 1.33 (d, J=6.4 Hz, 3H), 1.31-1.17 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.35, 159.33, 138.51, 129.49, 121.10, 116.18, 115.78, 99.98, 80.46, 74.39, 53.05, 47.47, 34.13, 31.07, 28.34, 19.66, 18.36; HRMS-ESI (m/z) ([M+Na]⁺) calcd for C₂₂H₃₁NO₅Na, 412.2094. found 412.2106.

Example 8 Step 1: Preparation of (3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-aminium chloride (F244)

A 25 mL screw top vial was charged with tert-butyl ((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamate (300 mg, 0.642 mmol), anhydrous CH₂Cl₂ (4 mL), and 4.0 M HCl in dioxane (3.21 mL, 12.83 mmol). After stirring at room temperature for 80 min, the reaction mixture was concentrated under a stream of nitrogen and dried under high vacuum to provide the title compound as a beige solid (259 mg, 100%): mp 200-210° C. (dec.); ¹H NMR (400 MHz, CDCl₃) δ 7.46-6.81 (m, 9H), 5.14 (s, 1H), 3.78-3.52 (m, 3H), 2.86 (s, 1H), 2.60-1.12 (m, 12H), 0.96 (s, 1H); ¹³C NMR (101 MHz, CD₃OD) δ 171.05, 160.65, 137.89, 136.19, 130.75, 129.87, 129.75, 122.14, 117.03, 81.89, 76.55, 68.05, 46.67, 37.46, 32.38, 27.71, 21.05, 20.12, 18.85; ESIMS m/z 369 ([M+H]⁺).

Example 8 Step 2: Preparation of 3-hydroxy-4-methoxy-N-((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)picolinamide (F49)

A 25 mL screw top vial was charged with (3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-aminium chloride (259 mg, 0.642 mmol), 3-hydroxy-4-methoxypicolinic acid (122 mg, 0.721 mmol), anhydrous CH₂Cl₂ (6.5 mL), and N,N-diisopropylethylamine (340 μL, 1.95 mmol). To the mixture was added PyBOP (376 mg, 0.723 mmol) and the reaction was stirred at room temperature for 1.5 h and then directly purified by column chromatography on SiO₂ (2→30% acetone/hexanes) to provide the title compound as a white solid (162 mg, 49%): mp 62-66° C.; ¹H NMR (400 MHz, CDCl₃) δ12.09 (s, 1H), 8.48 (d, J=8.2 Hz, 1H), 7.98 (d, J=5.1 Hz, 1H), 7.37-7.28 (m, 2H), 7.12-6.93 (m, 7H), 6.86 (d, J=5.2 Hz, 1H), 5.14 (dq, J=9.2, 6.4 Hz, 1H), 4.62 (dt, J=10.9, 7.4 Hz, 1H), 4.35 (t, J=8.9 Hz, 1H), 3.93 (s, 3H), 2.99 (dd, J=13.3, 3.2 Hz, 1H), 2.42-2.26 (m, 5H), 2.16-2.04 (m, 1H), 1.79-1.52 (m, 3H), 1.41-1.23 (m, 4H), 1.08-0.98 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 172.06, 168.59, 159.58, 155.27, 148.66, 140.47, 136.92, 135.38, 130.28, 129.63, 128.98, 128.59, 121.16, 115.48, 109.43, 81.02, 74.89, 55.99, 51.43, 45.59, 36.34, 33.47, 26.57, 20.95, 18.78, 18.33; ESIMS: m/z 519 ([M+H]⁺).

Example 9 Preparation of ((2-(((3S,7R,8R,9S)-7-(2-fluoroethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)carbamoyl)-4-methoxypyridin-3-yl)oxy)methyl acetate (F128)

To a solution of N-((3S,7R,8R,9S)-7-(2-fluoroethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide (97 mg, 0.220 mmol) in anhydrous acetone (2.2 mL) were added powdered K₂CO₃ (60.9 mg, 0.440 mmol) and bromomethyl acetate (32.4 μl, 0.330 mmol). The resulting mixture was heated to 50° C. and stirred vigorously for 16 h, then filtered through a plug of Celite®, concentrated, and purified by column chromatography on SiO₂ (5→50% acetone/hexanes) to provide the title compound as a sticky solid (87 mg, 77%): ¹H NMR (400 MHz, CDCl₃) δ 8.34 (d, J=8.1 Hz, 1H), 8.28 (d, J=5.4 Hz, 1H), 6.95 (d, J=5.4 Hz, 1H), 5.74 (s, 2H), 4.90 (dq, J=9.1, 6.4 Hz, 1H), 4.58 (ddt, J=9.4, 5.9, 4.6 Hz, 2H), 4.50-4.39 (m, 1H), 3.91 (s, 3H), 3.45 (dd, J=8.4, 6.6 Hz, 1H), 3.26 (dd, J=8.4, 6.4 Hz, 1H), 3.14-3.02 (m, 1H), 2.36 (dt, J=12.9, 6.7 Hz, 1H), 2.07 (s, 3H), 2.06-1.98 (m, 1H), 1.84 (dp, J=13.4, 6.7 Hz, 1H), 1.78-1.60 (m, 4H), 1.57 (s, 1H), 1.42 (d, J=6.4 Hz, 3H), 1.39-1.29 (m, 1H), 1.10 (dd, J=14.3, 5.7 Hz, 1H), 0.92 (d, J=6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 170.35, 167.84, 160.52, 157.81, 143.31, 141.51, 140.02, 107.14, 87.11, 81.42, 81.36, 79.73, 77.78, 72.81, 53.74, 49.43, 37.34, 37.30, 31.13, 29.17, 28.98, 26.73, 26.26, 18.44, 17.02, 16.98, 16.74, 15.69; HRMS-ESI (m/z) ([M+Na]⁺) calcd for C₂₅H₃₇FN₂O₈Na, 535.2426. found 535.2423.

Example 10 Preparation of 4-methoxy-2-(((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamoyl)pyridin-3-yl acetate (F79)

A 25 mL screw top vial was charged with 3-hydroxy-4-methoxy-N-((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)picolinamide (74.0 mg, 0.143 mmol), DMAP (19.4 mg, 0.159 mmol), 1,2-dichloroethane (DCE; 1 mL), acetyl chloride (20 μL, 0.281 mmol), and NEt₃ (70 μL, 0.502 mmol). The resulting mixture was heated to 50° C. for 7 h. After cooling to room temperature, the crude reaction mixture was directly purified by column chromatography on SiO₂ (2→40% acetone/hexanes) to provide the title compound as a white solid (56.0 mg, 70%): mp 96-100° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.53 (d, J=8.4 Hz, 1H), 8.33 (d, J=5.5 Hz, 1H), 7.36-7.27 (m, 2H), 7.12-6.92 (m, 8H), 5.12 (dq, J=9.1, 6.4 Hz, 1H), 4.63 (dt, J=10.9, 7.5 Hz, 1H), 4.33 (t, J=8.9 Hz, 1H), 3.89 (s, 3H), 2.97 (dd, J=13.3, 3.2 Hz, 1H), 2.41 (s, 3H), 2.32 (d, J=9.3 Hz, 5H), 2.14-2.03 (m, 1H), 1.73-1.48 (m, 3H), 1.39-1.19 (m, 5H); ¹³C NMR (101 MHz, CDCl₃) δ 172.55, 168.83, 162.34, 159.62, 159.36, 146.65, 141.31, 137.42, 137.01, 135.34, 129.62, 128.96, 128.61, 121.12, 115.50, 109.76, 81.10, 74.64, 56.22, 51.52, 45.62, 36.35, 33.75, 26.67, 20.95, 20.69, 18.83, 18.31; ESIMS: m/z 561 ([M+H]⁺).

Example 11 Preparation of 2-(((3S,7R,8R,9S)-8-(cyclopropylmethoxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)carbamoyl)-4-methoxypyridin-3-yl 3-methoxypropanoate (F195)

To a 4 mL vial were added N-((3S,7R,8R,9S)-8-(cyclopropylmethoxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide (85 mg, 0.166 mmol), CH₂Cl₂ (1 mL) and NEt₃ (0.069 mL, 0.497 mmol), 3-methoxypropanoyl chloride (30.5 mg, 0.249 mmol), and DMAP (3 mg, 0.02 mmol), and the resulting light yellow solution was stirred at room temperature overnight. The reaction mixture was concentrated and purified by column chromatography on SiO₂ (0→100% EtOAc/hexanes) to provide the title compound as a colorless semi-solid (77.8 mg, 78%): IR (neat) 3381, 2936, 1769, 1742, 1678, 1511, 1246, 1111 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.47 (d, J=7.3 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.09 (d, J=8.6 Hz, 2H), 6.98 (d, J=5.5 Hz, 1H), 6.83 (d, J=8.6 Hz, 2H), 4.91 (dq, J=9.1, 6.4 Hz, 1H), 4.55 (ddd, J=10.9, 8.4, 7.0 Hz, 1H), 3.88 (s, 3H), 3.81 (t, J=6.6 Hz, 2H), 3.78 (s, 3H), 3.57 (dd, J=9.7, 7.0 Hz, 1H), 3.44 (dd, J=9.7, 6.8 Hz, 1H), 3.41 (s, 3H), 3.15 (t, J=9.0 Hz, 1H), 3.07 (dd, J=13.4, 3.3 Hz, 1H), 2.98 (t, J=6.6 Hz, 2H), 2.35-2.20 (m, 2H), 1.87-1.77 (m, 1H), 1.61-1.47 (m, 2H), 1.48-1.37 (m, 1H), 1.45 (d, J=6.4 Hz, 3H), 1.22-1.05 (m, 2H), 0.90-0.79 (m, 1H), 0.63-0.49 (m, 2H), 0.29-0.14 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 172.61, 169.39, 162.32, 159.40, 157.82, 146.76, 141.45, 137.29, 132.66, 129.73, 113.77, 109.78, 83.79, 78.71, 75.22, 67.58, 58.78, 56.30, 55.22, 51.47, 46.17, 35.92, 34.62, 33.89, 26.55, 18.73, 18.08, 11.18, 3.16, 3.00; HRMS-ESI (m/z) ([M]⁺) calcd for C₃₂H₄₂N₂O₉, 598.2890. found, 598.2914.

Example 12 Preparation of ((2-(((3S,7R,8R,9S)-7-(cyclopentylmethyl)-8-(cyclopropylmethoxy)-9-methyl-2-oxooxonan-3-yl)carbamoyl)-4-methoxypyridin-3-yl)oxy)methyl isobutyrate (F154)

To a mixture of N-((3S,7R,8R,9S)-7-(cyclopentylmethyl)-8-(cyclopropylmethoxy)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide (60 mg, 0.126 mmol) and K₂CO₃ (34.9 mg, 0.253 mmol) in acetone (1 mL) was added chloromethyl isobutyrate (34.5 mg, 0.253 mmol) and the reaction was heated to 60° C. After TLC analysis indicated full consumption of the picolinamide starting material, the mixture was concentrated under a stream of N₂ and the residue purified by column chromatography on SiO₂ (gradient, EtOAc/hexanes) to yield the title compound as a colorless semi-solid (60.4 mg, 83%): IR (thin film) 3381, 2942, 1745, 1678, 1506, 974 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.38 (d, J=8.2 Hz, 1H), 8.27 (d, J=5.3 Hz, 1H), 6.93 (d, J=5.4 Hz, 1H), 5.81-5.61 (m, 2H), 4.89 (dd, J=9.2, 6.3 Hz, 1H), 4.57 (dt, J=11.0, 7.5 Hz, 1H), 3.89 (s, 3H), 3.50 (dd, J=9.6, 7.0 Hz, 1H), 3.36 (dd, J=9.6, 6.9 Hz, 1H), 3.01 (t, J=9.0 Hz, 1H), 2.54 (p, J=7.0 Hz, 1H), 2.36 (dd, J=13.1, 6.8 Hz, 1H), 1.92-1.43 (m, 15H), 1.42 (d, J=6.5 Hz, 2H), 1.35-1.19 (m, 2H), 1.14 (d, J=7.0 Hz, 3H), 1.17-0.92 (m, 5H), 0.62-0.48 (m, 2H), 0.29-0.17 (m, 2H); HRMS-ESI (m/z) ([M]⁺) calcd for C₃₁H₄₆N₂O₈, 574.3254. found, 574.3262.

Example 13 Preparation of ((4-methoxy-2-(((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl)carbamoyl)pyridin-3-yl)oxy)methyl 2-ethoxyacetate (F190)

To a 25 mL screw top vial were added 3-hydroxy-4-methoxy-N-((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl)picolinamide (87.9 mg, 0.159 mmol), Na₂CO₃ (33.8 mg, 0.319 mmol), NaI (6.3 mg, 0.264 mmol), anhydrous acetone (2 mL), and chloromethyl 2-ethoxyacetate (40.8 mg, 1.68 mmol), and the resulting mixture was warmed to 40° C. and stirred for 17 h. The reaction was cooled to room temperature, concentrated under a stream of nitrogen, and purified by column chromatography on SiO₂ (2→40% acetone/hexanes) to provide the title compound as a colorless oil (58.8 mg, 52%): ¹H NMR (400 MHz, CDCl₃) δ 8.29 (d, J=8.1 Hz, 1H), 8.25 (d, J=5.4 Hz, 1H), 7.09 (d, J=7.9 Hz, 2H), 7.03 (d, J=8.0 Hz, 2H), 6.93 (d, J=5.4 Hz, 1H), 5.80 (s, 2H), 4.89 (dq, J=9.1, 6.4 Hz, 1H), 4.55 (dt, J=10.9, 7.4 Hz, 1H), 4.08 (s, 2H), 3.88 (s, 3H), 3.80 (dt, J=8.9, 6.1 Hz, 1H), 3.64-3.54 (m, 3H), 3.17 (t, J=9.0 Hz, 1H), 2.96 (dd, J=13.3, 3.4 Hz, 1H), 2.40-2.13 (m, 7H), 1.92-1.76 (m, 3H), 1.65-1.37 (m, 6H), 1.30-1.14 (m, 4H), 0.93-0.80 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 172.62, 169.97, 162.83, 160.09, 145.73, 143.81, 142.18, 137.20, 135.41, 129.02, 128.58, 131.42-122.86 (m), 109.65, 89.44, 84.20, 74.83, 71.60, 67.71, 67.10, 56.15, 51.69, 45.80, 36.42, 33.56, 30.73 (q, J=29.0 Hz), 26.62, 23.01 (q, J=3.1 Hz), 20.93, 18.75, 18.05, 14.94; ¹⁹F NMR (376 MHz, CDCl₃) δ −66.35, ESIMS: m/z 669 ([M+H]⁺).

Example 14 Preparation of (S)-benzyl 5-((2R,3R)-2-((S)-1-(benzyloxy)ethyl)-tetrahydrofuran-3-yl)-2-((tert-butoxycarbonyl)amino)pentanoate

To a solution of (2S,6R,7R,8S)-benzyl 8-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-7-(cyclopropylmethoxy)-6-(2-hydroxyethyl)nonanoate (570 mg, 0.976 mmol) in anhydrous CH₂Cl₂ (10 mL) at 0° C. were added CBr₄ (389 mg, 1.172 mmol) and triphenylphosphine (333 mg, 1.269 mmol). The resulting solution was stirred for 6 h, at which time UPLC-MS showed ˜50% conversion to the desired product. The reaction was allowed to warm to room temperature and stirred for 3 d. The mixture was concentrated and purified by column chromatography on SiO₂ (2→25% acetone/hexanes) to provide the title compound as a clear, colorless oil (399.6 mg, 80%): ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.28 (m, 9H), 7.28-7.21 (m, 1H), 5.20 (d, J=12.3 Hz, 1H), 5.11 (d, J=12.3 Hz, 1H), 5.00 (d, J=8.1 Hz, 1H), 4.62 (d, J=11.9 Hz, 1H), 4.49 (d, J=11.9 Hz, 1H), 4.42-4.26 (m, 1H), 3.78 (dd, J=8.3, 4.8 Hz, 2H), 3.56-3.40 (m, 2H), 1.96 (ddd, J=14.2, 10.0, 7.2 Hz, 2H), 1.76 (dd, J=8.8, 4.7 Hz, 1H), 1.68-1.55 (m, 1H), 1.49 (dd, J=7.8, 3.6 Hz, 2H), 1.44 (s, 9H), 1.39-1.33 (m, 1H), 1.32-1.21 (m, 2H), 1.18 (d, J=6.1 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 172.71, 155.37, 138.92, 135.43, 128.60, 128.43, 128.32, 128.29, 127.59, 127.41, 87.07, 79.88, 71.09, 67.77, 66.97, 53.39, 40.81, 33.92, 32.84, 32.66, 28.33, 24.04, 16.01; ESIMS m/z 412.3 ([M+H]⁺) for M-BOC.

Example 15 Step 1: Preparation of (phenylthio)methyl 2-ethoxyacetate

To a mixture of Cs₂CO₃ (29.5 g, 91 mmol) in DMF (150 mL) at 0° C. was added 2-ethoxyacetic acid (18.0 mL, 191 mmol), and the resulting mixture was heated at 70° C. for 30 min. The reaction was cooled to 0° C., chloromethyl phenylsulfide (10.56 mL, 79 mmol) was added, and the reaction was heated at 70° C. for 90 min. The mixture was cooled to room temperature, and then 0° C., before diluting with H₂O (200 mL; an exotherm was observed). The reaction mixture was divided into two equal portions and one portion was further diluted with water (400 mL) and extracted with Et₂O (200 mL×2, 100 mL×1). The combined organic extracts were diluted with hexane (100 mL) and washed successively with 1.0 M aqueous NaOH (100 mL) and brine (2×200 mL), dried over anhydrous MgSO₄, filtered, and concentrated. The second portion of the reaction mixture from above was processed in an identical fashion and the two lots were combined and concentrated in vacuo to afford the title compound as a yellow oil (12.28 g, 97%): ¹H NMR (400 MHz, CDCl₃) δ 7.48-7.41 (m, 2H), 7.31 (ddd, J=12.6, 7.9, 6.3 Hz, 3H), 5.51 (s, 2H), 4.11 (s, 2H), 3.59 (q, J=7.0 Hz, 2H), 1.24 (t, J=7.0 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.00, 134.35, 130.53, 129.16, 127.55, 68.46, 68.10, 67.32, 14.99; ESIMS: m/z 226 ([M]⁺).

Example 15 Step 2: Preparation of chloromethyl 2-ethoxyacetate

To a solution of (phenylthio)methyl 2-ethoxyacetate (17.28 g, 76 mmol) in CH₂Cl₂ (200 mL) at 0° C. was added a solution of sulfuryl chloride (7.36 mL, 92 mmol) in CH₂Cl₂ (50 mL) over a period of 15 min, and the reaction was stirred at room temperature for 90 min. The reaction was again cooled to 0° C. and treated with a second portion of sulfuryl chloride (7.36 mL, 92 mmol) in CH₂Cl₂ (50 mL) over a period of 15 min. The reaction was then warmed to 30° C., stirred for 1 hour, and then cooled back to 0° C. A solution of cyclohexene (24.5 mL, 242 mmol) in CH₂Cl₂ (50 mL) was added over a period of 10 min, during which gas evolution was observed. The reaction was stirred at room temperature for 90 min, stored at −20° C. overnight, and purified by vacuum distillation to give the target compound as a slightly yellow oil (11.33 g, 97%): by 58° C. at 6.8 mm Hg; ¹H NMR (400 MHz, CDCl₃) δ 5.77 (s, 2H), 4.16 (s, 2H), 3.62 (q, J=7.0 Hz, 2H), 1.27 (t, J=7.0 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 168.81, 68.59, 67.77, 67.48, 14.96.

Example 16 Preparation of N-((3S,7R,8R,9S)-7-(cyclohexylmethyl)-8-(cyclopropylmethoxy)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide (F9)

A high pressure reactor equipped with a stir bar was charged with a solution of N-((3S,7R,8R,9S)-8-(cyclopropylmethoxy)-7-(4-fluorobenzyl)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide (230 mg, 0.459 mmol) in THF (7 mL) and 5% rhodium on carbon (56.8 mg, 0.028 mmol). After the reactor was sealed and purged with H₂ (4×), the reaction was charged to ˜600 psi of H₂ at room temperature. The reactor was warmed to 70° C. and stirred for 29 h, cooled to room temperature, and the reaction mixture was filtered through a Celite® pad. The filtrate was concentrated and purified by column chromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as a white solid (60.8 mg, 27%): ¹H NMR (400 MHz, CDCl₃) δ 12.11 (d, J=0.6 Hz, 1H), 8.49 (d, J=8.2 Hz, 1H), 7.99 (d, J=5.2 Hz, 1H), 6.87 (d, J=5.2 Hz, 1H), 4.95-4.84 (m, 1H), 4.55 (ddd, J=10.7, 8.2, 7.0 Hz, 1H), 3.94 (s, 3H), 3.49 (dd, J=9.6, 7.0 Hz, 1H), 3.37 (dd, J=9.6, 6.8 Hz, 1H), 3.01 (t, J=8.8 Hz, 1H), 2.39-2.28 (m, 1H), 1.78-1.46 (m, 10H), 1.45 (d, J=7.0 Hz, 3H), 1.41-0.71 (m, 10H), 0.59-0.52 (m, 2H), 0.26-0.18 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 172.21, 168.62, 155.31, 148.69, 140.51, 130.42, 109.44, 84.33, 78.51, 75.66, 56.05, 51.49, 40.09, 38.30, 35.05, 34.59, 33.63, 32.34, 27.44, 26.68, 26.48, 26.15, 18.77, 18.10, 11.14, 3.16, 2.94; ESIMS m/z 489.3 ([M+H]⁺).

Example A Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Mycosphaerella graminicola; Anamorph: Septoria tritici; Bayer Code SEPTTR)

Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 110 ppm Triton X-100. The fungicide solutions were applied onto wheat seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Septoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. When disease symptoms were fully expressed on the 1^(st) leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.

Example B Evaluation of Fungicidal Activity: Wheat Brown Rust (Puccinia triticina; Synonym: Puccinia Recondite f. sp. Tritici; Bayer Code PUCCRT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22° C. with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example C Evaluation of Fungicidal Activity: Wheat Glume Blotch (Leptosphaeria nodorum; Bayer Code LEPTNO)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example D Evaluation of Fungicidal Activity: Apple Scab (Venturia inaequalis; Bayer Code VENTIN)

Apple seedlings (variety McIntosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 hr after fungicide treatment and kept in a 22° C. dew chamber with 100% RH for 48 hr, and then moved to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example E Evaluation of Fungicidal Activity: Grape Powdery Mildew (Uncinula necator; Bayer Code UNCINE)

Grape seedlings (variety Carignane) were grown in soil-less Metro mix, with one plant per pot, and used in the test when approximately one month old. Plants were inoculated 24 hr after fungicide treatment by shaking spores from infected leaves over test plants. Plants were maintained in a greenhouse set at 20° C. until disease was fully developed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example F Evaluation of Fungicidal Activity: Powdery Mildew of Cucumber (Erysiphe cichoracearum; Bayer Code ERYSCI)

Cucumber seedlings (variety Bush Pickle) were grown in soil-less Metro mix, with one plant per pot, and used in the test when 12 to 14 days old. Plants were inoculated with a spore suspension 24 hr following fungicide treatments. After inoculation the plants remained in the greenhouse set at 20° C. until disease was fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example G Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer Code CERCBE)

Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 hr after fungicide treatments. Inoculated plants were kept in a dew chamber at 22° C. for 48 hr then incubated in a greenhouse set at 24° C. under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example H Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer Code PHAKPA)

Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 0.011% Tween 20. The fungicide solutions were applied onto soybean seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling.

Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22° C. and 100% RH then transferred to a growth room at 23° C. for disease to develop. Disease severity was assessed on the sprayed leaves.

Example I Evaluation of Fungicidal Activity: Wheat Powdery Mildew (Blumeria graminis f. Sp. Tritici; Synonym: Erysiphe graminis f. Sp. Tritici; Bayer Code ERYSGT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated by dusting with infected stock plants 24 hr after fungicide treatments. After inoculation the plants were kept in a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example J Evaluation of Fungicidal Activity: Barley Powdery Mildew (Blumeria graminis f. Sp. Hordei; Synonym: Erysiphe graminis f. Sp. Hordei; Bayer Code ERYSGH)

Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by dusting with infected stock plants 24 hr after fungicide treatments. After inoculation the plants were kept in a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example K Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer Code RHYNSE)

Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 20° C. with 100% relative humidity for 48 hr. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example L Evaluation of Fungicidal Activity: Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae; Bayer Code PYRIOR)

Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example M Evaluation of Fungicidal Activity: Tomato Early Blight (Alternaria solani; Bayer Code ALTESO)

Tomato plants (variety Outdoor girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example N Evaluation of Fungicidal Activity: Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer Code COLLLA)

Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

TABLE 1 Compound Structure and Appearance Prepared According Compound To Number Structure Example Appearance F1

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7; Step 2a; Example 8, Steps 1, 2 Colorless Solid F2

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F3

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2 White Solid F4

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F5

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F6

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2 Pale Yellow Sticky Solid F7

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 6; Example 8, Steps 1, 2 Colorless Thick Oil F8

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2 Sticky Colorless Oil F9

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2 White Solid F10

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2 White Solid F11

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2 Colorless Solid F12

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Step 1; Example 8, Steps 1, 2 White Solid F13

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F14

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2 Colorless Solid F15

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2 White Solid F16

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2 White Solid F17

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2 White Solid F18

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2 White Solid F19

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, Example 8, Steps 1, 2 Thick Oil F20

Example 1, Steps 1, 2a, 3, 4, 5b, 6, Example 8, Steps 1, 2 White Solid F21

Example 1, Steps 1, 2b, 3, 4, 5b, 6; Example 2, Step 1b; Example 8, Steps 1, 2 White Solid F22

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b; Example 3 Steps 1, 2a, Example 8, Steps 1, 2 White Solid F23

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2 White Solid F24

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2 Foam F25

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2; Example 16 White Solid F26

Example 8, Steps 1, 2 Colorless Semi- Solid F27

Example 8, Steps 1, 2 White Solid F28

Example 8, Steps 1, 2 Colorless Oil F29

Example 8, Steps 1, 2 White Solid F30

Example 8, Steps 1, 2 White Solid F31

Example 8, Steps 1, 2 White Solid F32

Example 8, Steps 1, 2 Colorless Semi Solid F33

Example 8, Steps 1, 2 Colorless Semi- Solid F34

Example 8, Steps 1, 2 White Solid F35

Example 8, Steps 1, 2 Light Yellow Solid F36

Example 8, Steps 1, 2 White Solid F37

Example 8, Steps 1, 2 White Solid F38

Example 8, Step 1 Step 2 White Solid F39

Example 8, Steps 1, 2 White Solid F40

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b; Example 8, Steps 1, 2 Colorless Thick Oil F41

Example 8 White Solid F42

Example 8 Colorless Oil F43

Example 8, Step 2 White Solid F44

Example 8, Step 2 White Solid F45

Example 8, Step 2 White Solid F46

Example 8, Step 2 White Solid F47

Example 8, Step 2 White Solid F48

Example 8, Step 2 White Solid F49

Example 8 White Solid F50

Example 8, Step 2 White Solid F51

Example 8, Step 2 Hard White Foam F52

Example 8 White Solid F53

Example 8, Step 2 White Solid F54

Example 8, Step 2 Sticky Glassy Solid F55

Example 8 White Solid F56

Example 8 Colorless Oil F57

Example 8, Step 2 White Solid F58

Example 8, Step 2 White Solid F59

Example 8 White Solid F60

Example 8 White Solid F61

Example 8, Step 2 Yellow Solid F62

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7; Step 2a; Example 8, Steps 1, 2; Example 10 Yellow Solid F63

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 10 Yellow Oil F64

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 10 Yellow Solid F65

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 10 Crystalline Yellow Solid F66

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 6; Example 8, Steps 1, 2; Example 10 Yellow Solid F67

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 10 Yellow Oil F68

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 10 Yellow Oil F69

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2; Example 10 Pale Yellow Solid F70

Example 10 Colorless Thick Oil F71

Example 10 Colorless Oil F72

Example 10 White Solid F73

Example 10 Sticky Yellow Semi Solid F74

Example 10 Sticky White Solid F75

Example 10 White Solid F76

Example 10 White Glassy Solid F77

Example 10 White Solid F78

Example 10 White Solid F79

Example 10 White Solid F80

Example 10 Hard White Foam F81

Example 10 White Solid F82

Example 10 White Solid F83

Example 10 White Solid F84

Example 10 White Solid F85

Example 10 White Solid F86

Example 10 White Solid F87

Example 10 White Foam F88

Example 10 White Foam F89

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7; Step 2a; Example 8, Steps 1, 2; Example 9 Colorless Solid F90

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Colorless Oil F91

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 9 Colorless Oil F92

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Thick Colorless Oil F93

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F94

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow Sticky Solid F95

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 6; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F96

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2; Example 9 Colorless Oil F97

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 16; Example 9 Pale Yellow Oil F98

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F99

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F100

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Step 1; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F101

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F102

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F103

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F104

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2; Example 9 Colorless Oil F105

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F106

Example 9 Thick Oil F107

Example 9 Sticky Oil F108

Example 9 White Solid F109

Example 9 Sticky White Foam F110

Example 9 White Foam F111

Example 9 White Foam F112

Example 9 White Foam F113

Example 9 Colorless Thick Oil F114

Example 9 Colorless Semi- Solid F115

Example 9 Yellow Oil F116

Example 9 Sticky White Solid F117

Example 9 Colorless Semi Solid F118

Example 9 Colorless Semi Solid F119

Example 9 Light Yellow Oil F120

Example 9 Colorless Solid F121

Example 9 Colorless Oil F122

Example 9 Colorless Oil F123

Example 9 Colorless Oil F124

Example 9 White Glassy Solid F125

Example 9 Solid F126

Example 9 White Oil F127

Example 9 White Solid F128

Example 9 White Solid F129

Example 9 White Solid F130

Example 9 White Solid F131

Example 9 Sticky Yellow Solid F132

Example 9 Sticky Oil F133

Example 9 Sticky Solid F134

Example 9 White Solid F135

Example 9 White Solid F136

Example 9 Yellow Solid F137

Example 9 Colorless Oil F138

Example 9 White Solid F139

Example 9 Colorless Oil F140

Example 9 Colorless Oil F141

Example 9 White Solid F142

Example 9 White Solid F143

Example 9 White Solid F144

Example 9 Off White Solid F145

Example 9 Off White Solid F146

Example 9 White Solid F147

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7; Step 2a; Example 8, Steps 1, 2; Example 12 Colorless Oil F148

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 12 Pale Yellow Oil F149

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 12 Yellow Oil F150

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 12 Sticky Yellow Solid F151

Example 12 White Solid F152

Example 12 Thick Oil F153

Example 11 Colorless Oil F154

Example 12 Colorless Semi Solid F155

Example 12 White Glassy Solid F156

Example 12 Colorless Oil F157

Example 12 White Solid F158

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7; Step 2a; Example 8, Steps 1, 2; Example 13 Colorless Oil F159

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 13 White Sticky Solid F160

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 13 Colorless Sticky Solid F161

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Colorless Oil F162

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Yellow Oil F163

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 6; Example 8, Steps 1, 2; Example 13 Colorless Oil F164

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 13 Colorless Oil F165

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example 13 Colorless Solid F166

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Step 1; Example 8, Steps 1, 2; Example 13 Colorless Oil F167

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Colorless Oil F168

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Colorless Oil F169

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2; Example 13 Colorless Oil F170

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2; Example 13 Pale Yellow Oil F171

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Steps 1, 2; Example 13 White Solid F172

Example 13 Colorless Thick Oil F173

Example 13 Colorless Thick Oil F174

Example 13 White Foam F175

Example 13 Colorless Thick Oil F176

Example 13 Colorless Oil F177

Example 13 Sticky White Solid F178

Example 13 Colorless Semi- Solid F179

Example 13 Colorless Oil F180

Example 13 White Solid F181

Example 13 Sticky Solid F182

Example 13 White Solid F183

Example 13 White Solid F184

Example 13 Colorless Film F185

Example 13 Colorless Film F186

Example 13 Colorless Film F187

Example 13 Colorless Oil F188

Example 13 Colorless Film F189

Example 13 White Solid F190

Example 13 Colorless Oil F191

Example 13 Colorless Oil F192

Example 13 White Solid F193

Example 13 White Solid F194

Example 11 Colorless Semi Solid F195

Example 11 Colorless Semi- Solid F196

Example 10 White Solid F197

Example 11 White Foam F198

Example 11 White Foam F199

Example 1, Steps 1, 2a, 3, 5b, 5c, 6 White Solid F200

Example 1, Steps 1, 2b, 3, 5b, 5c, 6 Colorless Oil F201

Example 1, Steps 1, 2b, 3, 5b, 5c, 6 Colorless Solid F202

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a Colorless Oil F203

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a White Solid F204

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a Colorless Oil F205

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 6 White Solid F206

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5 Colorless Thick Oil F207

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6 Colorless Foam F208

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6 Colorless Solid F209

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Step 1 Pale Yellow Oil F210

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a Colorless Oil F211

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a Colorless Oil F212

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2b- 1, 2b-2 White Solid F213

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5 Colorless Oil F214

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5 Colorless Oil F215

Example 1, Steps 1, 2a, 3, 4, 5a, 5c, 6 Colorless Semi Solid F216

Example 1, Steps 1, 2a, 3, 4, 5a, 5c, 6 White Foam F217

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Step 1a- 1, 1a-2; Example 5 Yellow Solid F218

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Steps 1a- 1, 1a-2; Example 4 Colorless Oil F219

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Thick Colorless Oil F220

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Steps 1, 2; Example 3 Colorless Oil F221

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Steps 1, 2; Example 3 Colorless Oil F222

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Colorless Oil F223

Example 1, Step 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Step 1, 2; Example 5 Yellow Solid F224

Example 1, Step 1 2a, 3, 4, 5a, 5b, 6 White Solid F225

Example 1, Step 1 2a, 3, 4, 5a, 5b, 6 Thick Oil F226

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b White Solid F227

Example 1, Steps 1, 2b, 3, 4, 5b, 6 Colorless Oil F229

Example 1 White Solid F230

Example 2, Step 1b White Solid F231

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 White Solid F232

Example 1, Steps 1, 2b, 3, 4, 5b, 6; Example 2, Step 1b White Solid F233

Example 1, Steps 1, 2b, 3, 4, 5b, 6 White Solid F234

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Oily White Solid F235

Example 7, Step 2e — F236

Example 1 White Solid F237

Example 1, Steps 1, 2b, 3, 4, 5b, 6 White Solid F238

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b; Example 3 Steps 1, 2a, Colorless Oil F239

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Colorless Semi Solid F240

Example 7, Step 2a — F241

Example 1, Steps 1, 2a, 3, 4, 5b, 6 White Foam F242

Example 7, Step 2b — F243

Example 7, Step 2b White Solid F244

Example 1 White Solid F245

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7, Step 2a Colorless Sticky Oil F246

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a Colorless Oil F247

Example 7, Step 2d-2 — F248

Example 1 Colorless Oil F249

Example 7, Step 2d-1 White Foam F250

Example 7, Step 2d-2 White Solid F251

Example 1, Step 6 Oil F253

Example 2, Step 1b Colorless Oil F254

Example 2, Step 1a-1, 1a-2 Yellow Solid F255

Example 3 Colorless Oil F256

Example 3 Colorless Oil F257

Example 1, Step 6 Sticky Oil F258

Example 1, Step 6 White Solid F259

Example 7, Step 2f-2 Orange Solid F260

Example 5 White Solid F261

Example 3 Colorless Oil F262

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 7; Step 2a; Example 8, Step 1 White Solid F263

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Step 1 White Solid F264

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Step 1 White Solid F265

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Step 1 White Solid F266

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Step 1 White Solid F267

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3; Steps 1, 2a; Example 8, Step 1 Pale Yellow Thick Oil F268

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 6; Example 8, Step 1 White Solid F269

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Step 1 White Sticky Solid F271

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Step 1 White Solid F272

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Step 1 Colorless Solid F273

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Step 1; Example 8, Step 1 Off- White Solid F274

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Step 1 White Solid F275

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2a; Example 8, Step 1 White Solid F276

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Step 1 White Solid F277

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Step 1 White Solid F278

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2; Example 5; Example 8, Step 1 White Solid F279

Example 8 Step 1 White Solid F280

Example 8 Step 1 White Solid F281

Example 8 Step 1 White Solid F282

Example 8 Step 1 White Solid F283

Example 8 Step 1 White Solid F284

Example 8 Step 1 White Solid F285

Example 8 Step 1 White Solid F287

Example 8, Step 1 White Solid F288

Example 8, Step 1 White Solid F289

Example 8, Step 1 White Solid F290

Example 8, Step 1 White Solid F291

Example 8, Step 1 White Solid F292

Example 8, Step 1 White Solid F293

Example 8, Step 1 Colorless Semi- Solid F294

Example 8, Step 1 Colorless Semi- Solid F295

Example 8, Step 1 White Solid F296

Example 8, Step 1 Orange Solid F297

Example 8, Step 1 White Solid F298

Example 8, Step 1 White Solid F299

Example 8, Step 1 White Solid F300

Example 8, Step 1 White Solid F301

Example 8, Step 1 White Solid F302

Example 8 White Solid F303

Example 8, Step 1 White Solid F304

Example 8, Step 1 White Solid F305

Example 8, Step 1 White Solid F306

Example 8, Step 1 — F307

Example 8, Step 1 Yellow Solid F308

Example 8 Beige Solid F309

Example 8, Step 1 White Solid F310

Example 8, Step 1 White Solid F311

Example 8 White Solid F312

Example 8, Step 1 White Solid F313

Example 8, Step 1 — F314

Example 8, Step 1 White Solid F315

Example 8, Step 1 — F316

Example 8 Tacky White Solid F317

Example 8 White Solid F318

Example 8, Step 1 White Solid F319

Example 8, Step 1 White Solid F320

Example 8, Step 1 — F321

Example 8 White Solid F322

Example 8 White Solid

TABLE 2 Analytical Data Cmpd. MP IR ¹³C or ¹⁹F No. (° C.) (cm⁻¹) MASS ¹H NMR NMR F1 57-59 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ 3366, (m/z) 1H), 8.53 (d, J = 8.2 Hz, 1H), 172.22, 168.65, 2949, ([M]⁺) 7.99 (d, J = 5.2 Hz, 1H), 159.68, 155.33, 1743, calcd for 7.33-7.24 (m, 2H), 7.00-6.91 (m, 148.71, 140.54, 1649, C₂₇H₃₆N₂O₆, 3H), 6.87 (d, J = 5.2 Hz, 1H), 130.38, 129.59, 1529, 484.2573; 5.15-5.04 (m, 1H), 4.61 (ddd, 121.01, 115.48, 1482, found, J = 10.8, 8.1, 6.9 Hz, 1H), 109.49, 81.55, 75.13, 1209 484.2576 4.27-4.18 (m, 1H), 3.93 (s, 3H), 56.06, 51.56, 43.20, 2.46-2.33 (m, 1H), 36.39, 33.54, 28.26, 1.93-1.35 (m, 7H), 1.32 (d, J = 6.5 Hz, 27.87, 27.51, 23.04, 3H), 1.29-1.05 (m, 4H), 22.05, 18.88, 18.41 0.81 (d, J = 6.6 Hz, 3H), 0.80 (d, J = 6.5 Hz, 3H) F2 131-133 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.12 (s, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.52 (d, J = 8.2 Hz, 1H), 172.25, 168.60, 2954, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.27, 148.65, 1742, calcd for 6.86 (d, J = 5.2 Hz, 1H), 140.48, 130.38, 1650, C₂₅H₄₀N₂O₆, 4.96-4.82 (m, 1H), 4.56 (dt, J = 10.5, 109.43, 84.23, 80.42, 1530, 464.2886; 7.4 Hz, 1H), 3.93 (s, 3H), 75.68, 56.02, 51.51, 1450, found, 3.46 (dd, J = 8.4, 6.3 Hz, 1H), 43.50, 36.53, 33.54, 1265 464.2891 3.27 (dd, J = 8.4, 6.5 Hz, 1H), 29.17, 28.08, 28.01, 3.07-2.96 (m, 1H), 27.52, 22.96, 22.26, 2.41-2.25 (m, 1H), 1.96-1.31 (m, 19.50, 19.45, 18.80, 7H), 1.43 (d, J = 6.4 Hz, 3H), 18.16 1.31-0.95 (m, 5H), 0.95-0.78 (m, 12H) F3 118-120 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (s, ¹³C NMR (CDCl₃) δ 3366, (m/z) 1H), 8.50 (d, J = 8.1 Hz, 1H), 172.22, 168.61, 2949, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.30, 148.67, 1743, calcd for 6.87 (d, J = 5.2 Hz, 1H), 140.51, 130.40, 1649, C₂₅H₃₈N₂O₆, 4.96-4.84 (m, 1H), 4.55 (ddd, J = 10.6, 109.44, 84.29, 78.63, 1583, 462.2730; 8.1, 7.0 Hz, 1H), 3.94 (s, 75.66, 56.05, 51.49, 1482, found, 3H), 3.56-3.33 (m, 2H), 43.55, 36.42, 33.59, 1209 462.2742 3.10-2.99 (m, 1H), 2.41-2.26 (m, 28.06, 27.32, 23.02, 1H), 1.82-1.31 (m, 7H), 22.21, 18.70, 18.11, 1.44 (d, J = 6.4 Hz, 3H), 11.12, 3.08, 3.02 1.31-0.93 (m, 5H), 0.90 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.62-0.51 (m, 2H), 0.27-0.17 (m, 2H) F4 101-103 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.50 (d, J = 8.2 Hz, 172.26, 168.62, 2937, ([M]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.32, 148.70, 1740, calcd for 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.51, 130.44, 1649, C₂₄H₃₈N₂O₆, 4.97-4.82 (m, 1H), 4.55 (ddd, 109.44, 84.52, 75.68, 1527, 450.2730; J = 10.7, 8.2, 7.0 Hz, 1H), 75.44, 56.06, 51.52, 1449, found, 3.94 (s, 3H), 3.69-3.59 (m, 1H), 43.49, 36.50, 33.62, 1263 450.2745 3.52-3.41 (m, 1H), 28.10, 27.46, 23.54, 3.09-2.97 (m, 1H), 2.40-2.27 (m, 23.03, 22.22, 18.77, 1H), 1.83-1.30 (m, 9H), 18.12, 10.71 1.43 (d, J = 6.4 Hz, 3H), 1.30-0.95 (m, 4H), 0.94 (t, J = 7.5 Hz, 3H), 0.89 (d, J = 6.7 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F5 49-51 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.51 (d, J = 8.2 Hz, 1H), 172.20, 168.63, 2950, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.30, 148.67, 1741, calcd for 6.87 (d, J = 5.2 Hz, 1H), 140.52, 130.35, 1650, C₂₅H₃₇F₃N₂O₆, 4.95-4.82 (m, 1H), 4.56 (ddd, J = 10.6, 127.16 (q, J = 276.0 Hz), 1528, 518.2604; 8.2, 7.0 Hz, 1H), 3.94 (s, 109.46, 84.75, 75.28, 1450, found, 3H), 3.81-3.68 (m, 1H), 71.54, 56.02, 51.49, 1279 518.2602 3.62-3.48 (m, 1H), 3.11-2.97 (m, 43.43, 36.44, 33.49, 1H), 2.40-2.28 (m, 1H), 30.77 (q, J = 29.0 Hz), 2.28-2.12 (m, 2H), 1.95-1.32 (m, 28.15, 28.05, 27.40, 9H), 1.41 (d, J = 6.5 Hz, 3H), 23.04 (q, J = 3.0 Hz), 1.31-0.94 (m, 4H), 22.93, 22.14, 18.75, 0.95-0.82 (m, 6H) 18.11 ¹⁹F NMR (CDCl₃) δ −66.41 F6 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 477.4 1H), 8.52 (d, J = 8.2 Hz, 172.42, 168.60, ([M + H]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.33, 148.70, 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.52, 130.47, 4.94-4.80 (m, 1H), 4.55 (ddd, 109.44 83.57, 82.83, J = 10.9, 8.1, 6.6 Hz, 1H), 76.11, 56.07, 51.77, 4.08-3.98 (m, 1H), 3.94 (s, 3H), 42.85, 36.86, 33.51, 3.81-3.58 (m, 1H), 3.14 (dd, 32.75, 32.50, 28.27, J = 9.1, 7.8 Hz, 1H), 23.04, 22.97, 22.96, 2.41-2.27 (m, 1H), 1.87-0.99 (m, 22.37, 19.15, 18.37 18H), 1.44 (d, J = 6.5 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F7 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3369, (m/z) 1H), 8.49 (d, J = 8.2 Hz, 172.20, 168.62, 2942, ([M]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.33, 148.70, 1742, calcd for 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.51, 130.43, 1650, C₂₂H₃₄N₂O₆, 4.95-4.80 (m, 1H), 4.56 (ddd, 109.45, 86.37, 75.42, 1530, 422.2417; J = 10.7, 8.2, 7.1 Hz, 1H), 61.23, 56.07, 51.49, 1482, found, 3.94 (s, 3H), 3.51 (s, 3H), 43.53, 36.48, 33.62, 1265 422.2427 3.03-2.88 (m, 1H), 2.41-2.26 (m, 28.24, 28.17, 27.21, 1H), 1.85-1.31 (m, 7H), 23.09, 22.17, 18.71, 1.44 (d, J = 6.4 Hz, 3H), 18.07 1.31-0.93 (m, 4H), 0.90 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H) F8 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3369, (m/z) 1H), 8.47 (d, J = 8.1 Hz, 176.20, 172.28, 2952, ([M]⁺) 1H), 7.99 (d, J = 5.2 Hz, 168.63, 155.36, 1734, calcd for 1H), 6.87 (d, J = 5.2 Hz, 1H), 148.75, 140.50, 1651, C₂₇H₄₀N₂O₇, 5.08-4.96 (m, 1H), 130.41, 109.47, 76.04, 1529, 504.2836; 4.94-4.83 (m, 1H), 4.59 (ddd, J = 10.8, 73.69, 56.08, 51.49, 1482, found, 8.1, 7.1 Hz, 1H), 3.94 (s, 44.10, 41.92, 36.35, 1265, 504.2861 3H), 2.81-2.67 (m, 1H), 33.46, 30.08, 30.00, 1176 2.44-2.31 (m, 1H), 2.01-1.33 (m, 28.00, 27.90, 27.40, 14H), 1.33-1.14 (m, 3H), 25.71, 25.70, 22.90, 1.27 (d, J = 6.3 Hz, 3H), 22.20, 18.68, 17.56 1.14-0.96 (m, 2H), 0.86 (d, J = 6.6 Hz, 3H), 0.85 (d, J = 6.6 Hz, 3H) F9 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 489.3 1H), 8.49 (d, J = 8.2 Hz, 172.21, 168.62, ([M + H]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.31, 148.69, 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.51, 130.42, 4.97-4.84 (m, 1H), 4.55 (ddd, 109.44, 84.33, 78.51, J = 10.7, 8.2, 7.0 Hz, 1H), 75.66, 56.05, 51.49, 3.94 (s, 3H), 3.49 (dd, J = 9.6, 7.0 Hz, 40.09, 38.30, 35.05, 1H), 3.37 (dd, J = 9.6, 6.8 Hz, 34.59, 33.63, 32.34, 1H), 3.07-2.95 (m, 1H), 27.44, 26.68, 26.48, 2.40-2.28 (m, 1H), 26.15, 18.77, 18.10, 1.80-1.44 (m, 11H), 1.43 (d, J = 6.4 Hz, 11.14, 3.16, 2.94 3H), 1.42-0.68 (m, 9H), 0.61-0.50 (m, 2H), 0.28-0.17 (m, 2H) F10 69-71 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3367, (m/z) 1H), 8.45 (d, J = 8.2 Hz, 172.09, 168.64, 2939, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 161.31 (d, J = 243.7 Hz), 1740, calcd for 1H), 7.17-7.08 (m, 2H), 155.33, 148.70, 1648, C₂₇H₃₃FN₂O₆, 7.02-6.93 (m, 2H), 6.86 (d, J = 5.2 Hz, 140.53, 136.24 (d, J = 3.2 Hz), 1528, 500.2323; 1H), 5.00-4.86 (m, 1H), 130.37, 1447, found, 4.56 (ddd, J = 10.9, 8.2, 7.0 Hz, 130.14 (d, J = 7.7 Hz), 1214, 500.2329 1H), 3.93 (s, 3H), 115.16 (d, J = 21.1 Hz), 1056 3.58 (dd, J = 9.7, 7.0 Hz, 1H), 109.47, 83.69, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 78.79, 75.46, 56.06, 3.21-3.14 (m, 1H), 3.14-3.07 (m, 51.41, 46.09, 36.06, 1H), 2.38-2.23 (m, 2H), 33.55, 26.61, 18.73, 1.91-1.77 (m, 1H), 1.64-1.51 (m, 18.10, 11.17, 3.16, 2H), 1.48-1.37 (m, 1H), 3.02 1.47 (d, J = 6.4 Hz, 3H), ¹⁹F NMR (CDCl₃) δ −117.38 1.32-1.20 (m, 1H), 1.18-1.06 (m, 1H), 0.96-0.82 (m, 1H), 0.65-0.53 (m, 2H), 0.31-0.19 (m, 2H) F11 88-90 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.07 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3370, (m/z) 1H), 8.48 (d, J = 8.2 Hz, 172.11, 168.68, 2939, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 161.33 (d, J = 243.7 Hz), 1745, calcd for 1H), 7.37-7.27 (m, 2H), 159.53, 155.36, 1650, C₂₉H₃₁FN₂O₆, 7.12-6.90 (m, 7H), 6.86 (d, J = 5.2 Hz, 148.74, 140.56, 1509, 522.2166; 1H), 5.21-5.07 (m, 1H), 135.77, (d, J = 3.2 Hz), 1327, found, 4.62 (ddd, J = 11.0, 8.2, 6.9 Hz, 130.34, 130.11 (d, J = 7.8 Hz), 1210 522.2182 1H), 3.93 (s, 3H), 129.75, 2.98 (dd, J = 13.5, 3.4 Hz, 1H), 121.32, 115.47, 2.44-2.27 (m, 2H), 115.16 (d, J = 21.1 Hz), 2.14-1.99 (m, 1H), 1.76-1.48 (m, 109.52, 80.93, 74.89, 3H), 1.38-1.21 (m, 2H), 56.08, 51.50, 45.70, 1.36 (d, J = 6.5 Hz, 3H), 36.12, 33.50, 26.77, 1.11-0.97 (m, 1H) 18.89, 18.38 ¹⁹F NMR (CDCl₃) δ −117.22 F12 65-67 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ 3366, (m/z) 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.10, 168.65, 2938, ([M]⁺) 7.97 (d, J = 5.2 Hz, 1H), 161.29 (d, J = 243.7 Hz), 1742, calcd for 7.17-7.06 (m, 2H), 7.02-6.92 (m, 155.32, 148.70, 1649, C₂₆H₃₁FN₂O₆, 2H), 6.86 (d, J = 5.2 Hz, 1H), 140.54, 136.20 (d, J = 3.2 Hz), 1529, 486.2166; 6.03-5.87 (m, 1H), 5.34 (dq, 134.28, 1218 found, J = 17.2, 1.6 Hz, 1H), 130.34, 130.13 (d, J = 7.7 Hz), 486.2172 5.21 (dq, J = 10.4, 1.3 Hz, 1H), 117.12, 5.00-4.88 (m, 1H), 4.57 (ddd, 115.14 (d, J = 21.1 Hz), J = 10.9, 8.2, 7.0 Hz, 1H), 109.50, 84.06, 4.29 (ddt, J = 12.2, 5.5, 1.5 Hz, 75.29, 74.68, 56.05, 1H), 4.11 (ddt, J = 12.3, 5.6, 51.42, 45.92, 36.08, 1.4 Hz, 1H), 3.93 (s, 3H), 33.49, 26.58, 18.75, 3.30-3.18 (m, 1H), 3.13-3.01 (m, 18.14 1H), 2.41-2.23 (m, 2H), ¹⁹F NMR (CDCl₃) δ −117.33 1.91-1.75 (m, 1H), 1.68-1.53 (m, 2H), 1.50-1.37 (m, 1H), 1.48 (d, J = 6.4 Hz, 3H), 1.37-1.17 (m, 1H), 0.98-0.81 (m, 1H) F13 127-129 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3367, (m/z) 1H), 8.45 (d, J = 8.2 Hz, 172.12, 168.64, 2937, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 161.30 (d, J = 243.7 Hz), 1741, calcd for 1H), 7.17-7.05 (m, 2H), 155.34, 148.71, 1649, C₂₆H₃₃FN₂O₆, 7.02-6.92 (m, 2H), 6.86 (d, J = 5.2 Hz, 140.53, 136.31 (d, J = 3.3 Hz), 1528, 488.2323; 1H), 4.99-4.86 (m, 1H), 130.39, 1508, found, 4.56 (ddd, J = 10.9, 8.2, 7.0 Hz, 130.13 (d, J = 7.7 Hz), 1217 488.2322 1H), 3.94 (s, 3H), 115.15 (d, J = 21.1 Hz), 3.81-3.66 (m, 1H), 3.52 (dt, J = 8.7, 109.47, 83.89, 6.7 Hz, 1H), 3.21-3.12 (m, 75.66, 75.48, 56.07, 1H), 3.11-3.01 (m, 1H), 51.43, 46.10, 36.01, 2.39-2.23 (m, 2H), 1.87-1.73 (m, 33.56, 26.61, 23.59, 1H), 1.71-1.52 (m, 4H), 18.77, 18.10, 10.74 1.47 (d, J = 6.5 Hz, 3H), ¹⁹F NMR (CDCl₃) δ- 1.46-1.36 (m, 1H), 1.33-1.18 (m, 117.43 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.95-0.83 (m, 1H) F14 71-73 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.12, 168.63, 2939, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 161.30 (d, J = 243.6 Hz), 1741, calcd for 7.17-7.04 (m, 2H), 7.02-6.91 (m, 155.34, 148.71, 1650, C₂₇H₃₅FN₂O₆, 2H), 6.86 (d, J = 5.2 Hz, 1H), 140.52, 136.35 (d, J = 3.2 Hz), 1529, 502.2479; 5.00-4.84 (m, 1H), 4.56 (ddd, 130.39, 1508, found, J = 11.0, 8.2, 7.0 Hz, 1H), 130.12 (d, J = 7.6 Hz), 1219 502.2485 3.94 (s, 3H), 3.56 (dd, J = 8.4, 6.3 Hz, 115.15 (d, J = 21.1 Hz), 1H), 3.34 (dd, J = 8.4, 6.5 Hz, 109.47, 83.62, 1H), 3.18-3.11 (m, 1H), 80.71, 75.51, 56.07, 3.11-3.01 (m, 1H), 51.44, 46.22, 35.92, 2.40-2.24 (m, 2H), 1.97-1.73 (m, 33.57, 29.27, 26.58, 2H), 1.68-1.52 (m, 2H), 19.52, 19.49, 18.80, 1.49-1.36 (m, 1H), 1.47 (d, J = 6.5 Hz, 18.17 3H), 1.33-1.19 (m, 1H), ¹⁹F NMR (CDCl₃) δ −117.44 0.97 (d, J = 6.7 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 0.93-0.83 (m, 1H) F15 164-166 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.12 (s, ¹³C NMR (CDCl₃) δ 3369, (m/z) 1H), 8.47 (d, J = 8.2 Hz, 1H), 171.96, 168.62, 2941, ([M]⁺) 7.96 (d, J = 5.2 Hz, 1H), 161.25 (d, J = 243.8 Hz), 1743, calcd for 7.19-7.05 (m, 2H), 7.03-6.91 (m, 155.26, 148.63, 1649, C₂₅H₂₉F₃N₂O₆, 2H), 6.86 (d, J = 5.2 Hz, 1H), 140.53, 135.81 (d, J = 3.2 Hz), 1529, 510.1978; 5.88 (tt, J = 55.1, 3.9 Hz, 1H), 130.19, 1509, found, 4.93 (dq, J = 9.4, 6.2 Hz, 1H), 130.09 (d, J = 7.7 Hz), 1217 510.1977 4.65-4.53 (m, 1H), 115.10 (d, J = 21.0 Hz), 4.07-3.91 (m, 1H), 3.91 (s, 3H), 113.87 (t, J = 241.0 Hz), 3.86-3.71 (m, 1H), 109.51, 3.31-3.19 (m, 1H), 3.09-2.98 (m, 85.27, 74.63, 72.49 (t, 1H), 2.42-2.22 (m, 2H), J = 27.5 Hz), 55.95, 1.90-1.76 (m, 1H), 1.71-1.48 (m, 51.29, 45.75, 35.77, 2H), 1.47 (d, J = 6.5 Hz, 3H), 33.32, 26.38, 18.65, 1.47-1.36 (m, 1H), 18.00 1.35-1.20 (m, 1H), 0.95-0.80 (m, ¹⁹F NMR (CDCl₃) δ −117.13, 1H) −125.48 (d, J = 9.4 Hz, 2F) F16 70-72 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.05 (s, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.43 (d, J = 8.1 Hz, 1H), 176.13, 172.14, 2946, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 168.65, 161.39 (d, J = 244.1 Hz), 1732, calcd for 7.11-7.02 (m, 2H), 7.01-6.92 (m, 155.36, 1649, C₂₉H₃₅FN₂O₇, 2H), 6.86 (d, J = 5.2 Hz, 1H), 148.75, 140.52, 1529, 542.2428; 5.13-4.92 (m, 2H), 4.60 (ddd, 135.50 (d, J = 3.2 Hz), 1509, found, J = 11.0, 8.1, 7.0 Hz, 1H), 130.34, 130.06 (d, J = 7.8 Hz), 1448, 542.2417 3.94 (s, 3H), 2.82-2.57 (m, 2H), 115.26 (d, J = 21.1 Hz), 1263 2.44-2.25 (m, 2H), 109.49, 2.04-1.43 (m, 11H), 1.38-1.18 (m, 75.44, 73.45, 56.08, 2H), 1.30 (d, J = 5.8 Hz, 3H), 51.40, 44.11, 44.01, 1.05-0.93 (m, 1H) 35.92, 33.37, 30.07, 30.05, 26.79, 25.73, 25.71, 18.66, 17.55 ¹⁹F NMR (CDCl₃) δ −117.01 F17 177-179 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.05 (s, ¹³C NMR (CDCl₃) δ 3370, (m/z) 1H), 8.44 (d, J = 8.1 Hz, 1H), 176.46, 172.13, 2939, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 168.65, 161.39 (d, J = 244.2 Hz), 1735, calcd for 7.12-7.02 (m, 2H), 7.02-6.91 (m, 155.36, 1650, C₂₇H₃₃FN₂O₇, 2H), 6.86 (d, J = 5.2 Hz, 1H), 148.74, 140.52, 1529, 516.2272; 5.13-4.96 (m, 2H), 4.61 (ddd, 135.46 (d, J = 3.2 Hz), 1509, found, J = 11.0, 8.1, 7.0 Hz, 1H), 130.33, 130.05 (d, J = 7.8 Hz), 1264 516.2257 3.94 (s, 3H), 2.70-2.62 (m, 1H), 115.27 (d, J = 21.1 Hz), 2.59 (hept, J = 7.0 Hz, 1H), 109.50, 2.43-2.28 (m, 2H), 75.38, 73.38, 56.07, 2.01-1.86 (m, 1H), 1.77-1.46 (m, 51.39, 44.09, 35.84, 3H), 1.35-1.20 (m, 1H), 34.22, 33.36, 26.71, 1.30 (d, J = 5.9 Hz, 3H), 1.22 (d, J = 7.0 Hz, 19.09, 19.00, 18.65, 3H), 1.22 (d, J = 7.0 Hz, 17.51 3H), 1.06-0.93 (m, 1H) ¹⁹F NMR (CDCl₃) δ −116.98 F18 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (s, ¹³C NMR (CDCl₃) δ m/z 485.4 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.16, 168.65, ([M + H]⁺) 7.96 (d, J = 5.2 Hz, 1H), 155.33, 148.71, 7.28 (dd, J = 10.2, 4.4 Hz, 2H), 140.78, 140.54, 7.23-7.12 (m, 3H), 6.85 (d, J = 5.2 Hz, 130.39, 128.86, 1H), 4.99-4.86 (m, 128.38, 125.93, 1H), 4.55 (tt, J = 25.8, 12.9 Hz, 109.48, 83.66, 80.66, 1H), 3.92 (s, 3H), 75.54, 56.06, 51.45, 3.56 (dd, J = 8.3, 6.3 Hz, 1H), 46.14, 36.73, 33.58, 3.34 (dd, J = 8.3, 6.6 Hz, 1H), 29.27, 26.55, 19.55, 3.19-3.08 (m, 2H), 2.42-2.22 (m, 19.50, 18.79, 18.19 2H), 1.97-1.78 (m, 2H), 1.69-1.52 (m, 2H), 1.51-1.41 (m, 5H), 0.96 (dt, J = 13.2, 6.6 Hz, 6H), 0.82-09.82 (m, 1H) F19 — — ESIMS ¹H NMR (CDCl₃) δ 12.12 (s, ¹³C NMR (75 MHz, m/z 483.5 1H), 8.47 (d, J = 8.2 Hz, 1H), CDCl₃) δ 172.01, ([M + H]⁺) 7.94 (d, J = 5.2 Hz, 1H), 168.54, 155.18, 7.35-7.23 (m, 2H), 7.18 (td, J = 6.4, 148.58, 140.54, 1.5 Hz, 3H), 6.84 (d, J = 5.3 Hz, 140.42, 130.22, 1H), 4.94 (dq, J = 9.1, 128.75, 128.26, 6.4 Hz, 1H), 4.57 (ddd, J = 10.9, 125.83, 109.42, 83.61, 8.2, 7.0 Hz, 1H), 3.90 (s, 78.59, 75.37, 55.93, 3H), 3.58 (dd, J = 9.7, 7.0 Hz, 51.34, 45.94, 36.79, 1H), 3.44 (dd, J = 9.7, 6.8 Hz, 33.42, 26.52, 18.65, 1H), 3.31-3.03 (m, 2H), 18.02, 11.11, 3.08, 2.41-2.19 (m, 2H), 1.88 (tt, J = 8.3, 2.94 4.0 Hz, 1H), 1.58 (ddt, J = 12.9, 6.9, 2.6 Hz, 2H), 1.47 (d, J = 6.4 Hz, 3H), 1.53-1.38 (m, overlapping, 1H), 1.30-1.20 (m, 1H), 1.17-1.02 (m, 1H), 0.99-0.78 (m, 1H), 0.69-0.48 (m, 2H), 0.25 (qd, J = 4.2, 1.7 Hz, 2H) F20 — — ESIMS ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 505.4 1H), 8.47 (d, J = 8.1 Hz, 172.24, 168.77, ([M + H]⁺) 1H), 7.98 (d, J = 5.2 Hz, 159.73, 155.46, 1H), 7.40-7.21 (m, 3H), 148.84, 140.65, 7.21-7.08 (m, 3H), 7.08-6.93 (m, 140.27, 130.46, 3H), 6.89-6.82 (m, 1H), 129.83, 128.91, 5.20-5.07 (m, 1H), 4.62 (ddd, J = 11.0, 128.47, 126.13, 8.2, 7.0 Hz, 1H), 4.36 (t, 121.38, 115.65, J = 8.9 Hz, 1H), 3.93 (s, 3H), 109.61, 81.17, 75.05, 3.78-3.62 (m, 1H), 3.03 (dd, 56.18, 51.61, 45.75, J = 13.3, 3.3 Hz, 1H), 37.00, 33.64, 26.80, 2.35 (ddd, J = 11.3, 9.4, 6.5 Hz, 18.98, 18.51 2H), 2.20-2.07 (m, 1H), 1.78-1.64 (m, 2H), 1.64-1.50 (m, 1H), 1.36 (d, J = 6.5 Hz, 3H), 1.34-1.27 (m, 1H), 1.08-0.97 (m, 1H) F21 — — ESIMS ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ m/z 471.4 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.26, 168.73, ([M + H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 155.43, 148.81, 7.33-7.24 (m, 2H), 7.23-7.13 (m, 140.83, 140.63, 3H), 6.85 (d, J = 5.2 Hz, 1H), 130.50, 128.96, 4.93 (dq, J = 9.2, 6.4 Hz, 1H), 128.47, 126.03, 4.56 (ddd, J = 11.0, 8.2, 7.0 Hz, 109.57, 84.05, 75.72, 1H), 3.93 (s, 3H), 75.62, 56.17, 51.55, 3.79-3.67 (m, 1H), 3.53 (dt, J = 8.7, 46.11, 36.93, 33.70, 6.7 Hz, 1H), 3.18 (t, J = 9.0 Hz, 26.69, 23.70, 18.87, 1H), 3.15-3.06 (m, 1H), 18.23, 10.86 2.41-2.23 (m, 2H), 1.86 (ddd, J = 12.1, 8.4, 3.9 Hz, 1H), 1.72-1.55 (m, 4H), 1.48 (d, J = 6.4 Hz, 3H), 1.45-1.38 (m, 1H), 1.33-1.19 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.94-0.82 (m, 1H) F22 — — ESIMS ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ m/z 497.4 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.34, 168.60, ([M + H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 155.32, 148.70, 7.38-7.23 (m, 2H), 7.22-7.13 (m, 141.05, 140.51, 3H), 6.85 (d, J = 5.2 Hz, 1H), 130.40, 128.87, 4.91 (dq, J = 9.1, 6.5 Hz, 1H), 128.37, 125.87, 4.54 (ddd, J = 11.1, 8.2, 6.6 Hz, 109.45, 83.87, 82.31, 1H), 4.18-4.06 (m, 1H), 75.95, 56.06, 51.68, 3.93 (s, 3H), 3.30 (t, J = 8.6 Hz, 45.22, 36.93, 33.42, 1H), 3.20 (dd, J = 13.3, 32.84, 32.57, 27.89, 3.3 Hz, 1H), 2.40-2.16 (m, 23.05, 22.99, 19.10, 2H), 1.87-1.67 (m, 7H), 18.39 1.66-1.52 (m, 4H), 1.49 (d, J = 6.5 Hz, 3H), 1.46-1.36 (m, 1H), 1.32-1.14 (m, 1H), 1.04-0.84 (m, 1H) F23 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 457.2 1H), 8.45 (d, J = 8.2 Hz, 172.15, 168.63, ([M + H]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.33, 148.71, 1H), 7.33-7.24 (m, 2H), 140.68, 140.52, 7.23-7.15 (m, 3H), 6.85 (d, J = 5.1 Hz, 130.40, 128.86, 1H), 4.93 (dq, J = 9.2, 6.4 Hz, 128.37, 125.94, 1H), 4.56 (ddd, J = 10.9, 109.46, 84.17, 75.48, 8.2, 7.0 Hz, 1H), 3.93 (s, 3H), 69.26, 56.07, 51.45, 3.83 (dq, J = 8.8, 6.9 Hz, 1H), 45.88, 36.92, 33.61, 3.64 (dq, J = 8.9, 7.0 Hz, 1H), 26.62, 18.74, 18.05, 3.24-3.15 (m, 1H), 3.11 (dd, 15.73 J = 13.3, 3.4 Hz, 1H), 2.44-2.20 (m, 2H), 1.85 1.90-1.79 (m, 1H), 1.68-1.53 (m, 2H), 1.52-1.41 (m, 1H), 1.48 (d, J = 6.5 Hz, 3H), 1.31-1.21 (m, 1H), 1.25 (t, J = 6.9 Hz, 3H), 0.95-0.83 (m, 1H) F24 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.6 Hz, ¹³C NMR (75 MHz, m/z 487.4 1H), 8.45 (d, J = 8.2 Hz, CDCl₃) δ 172.28, ([M + H]⁺) 1H), 7.97 (d, J = 5.2 Hz, 168.83, 155.52, 1H), 7.33-7.23 (m, 2H), 148.91, 140.89, 7.23-7.15 (m, 3H), 6.85 (dd, J = 5.3, 140.72, 130.59, 0.6 Hz, 1H), 4.96 (dq, J = 9.2, 129.09, 128.99, 6.4 Hz, 1H), 4.56 (ddd, J = 10.9, 128.55, 126.12, 8.2, 7.0 Hz, 1H), 109.68, 84.89, 75.53, 3.98-3.94 (m, 1H), 3.93 (s, 3H), 73.05, 72.36, 59.29, 3.73 (ddd, J = 10.4, 5.7, 3.5 Hz, 56.27, 51.64, 45.98, 1H), 3.62-3.53 (m, 2H), 37.00, 33.80, 26.79, 3.40 (s, 3H), 3.24 (t, J = 9.1 Hz, 18.99, 18.38 1H), 3.17 (dd, J = 13.2, 3.4 Hz, 1H), 2.43-2.24 (m, 2H), 1.98-1.85 (m, 1H), 1.60 (dtt, J = 9.1, 6.6, 3.2 Hz, 2H), 1.54-1.42 (m, 4H), 1.33-1.20 (m, 1H), 0.95-0.81 (m, 1H) F25 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 491.3 1H), 8.49 (d, J = 8.2 Hz, 172.25, 168.61, ([M + H]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.33, 148.70, 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.50, 130.45, 4.89 (dq, J = 9.2, 6.4 Hz, 1H), 109.44, 84.26, 80.38, 4.55 (ddd, J = 10.8, 8.2, 7.0 Hz, 75.75, 56.06, 51.53, 1H), 3.94 (s, 3H), 40.00, 38.14, 35.09, 3.46 (dd, J = 8.4, 6.1 Hz, 1H), 34.60, 33.65, 32.27, 3.24 (dd, J = 8.4, 6.6 Hz, 1H), 29.21, 27.42, 26.69, 2.98 (t, J = 8.8 Hz, 1H), 2.34 (dt, J = 13.2, 26.52, 26.20, 19.58, 6.7 Hz, 1H), 19.47, 18.81, 18.17 1.83 (hept, J = 6.5 Hz, 1H), 1.77-1.61 (m, 8H), 1.42 (d, J = 6.4 Hz, 3H), 1.40-1.08 (m, 8H), 1.02-0.93 (m, 8H), 0.76 (qd, J = 13.6, 12.2, 4.1 Hz, 1H) F26 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.07 (s, — Film) (m/z) 1H), 8.47 (d, J = 8.1 Hz, 1H), 3366, ([M]⁺) 7.99 (d, J = 5.1 Hz, 1H), 2938, calcd for 7.31 (dd, J = 8.7, 7.3 Hz, 2H), 1743, C₃₀H₃₄N₂O₇, 7.09-6.94 (m, 5H), 6.87 (d, J = 5.3 Hz, 1649, 534.2366; 1H), 6.80 (d, J = 8.7 Hz, 1530, found, 2H), 5.14 (dq, J = 9.3, 6.4 Hz, 1512, 534.2373 1H), 4.70-4.53 (m, 1H), 1243 4.34 (t, J = 8.9 Hz, 1H), 3.94 (s, 3H), 3.78 (s, 3H), 2.96 (dd, J = 13.8, 3.2 Hz, 1H), 2.33 (ddd, J = 17.7, 12.3, 9.0 Hz, 2H), 2.05 (s, 2H), 1.69 (dt, J = 10.7, 5.0 Hz, 2H), 1.38-1.25 (m, 1H), 1.36 (d, J = 6.5 Hz, 3H), 1.14-0.88 (m, 1H) F27 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.55 (d, J = 8.2 Hz, 1H), 172.21, 168.64, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 159.73, 155.35, calcd for 7.35-7.23 (m, 2H), 6.95 (d, J = 7.5 Hz, 148.72, 140.53, C₂₈H₃₆N₂O₆, 3H), 6.86 (d, J = 5.2 Hz, 130.40, 129.59, 496.2573; 1H), 5.10 (dq, J = 9.1, 6.5 Hz, 120.98, 115.55, found, 1H), 4.61 (ddd, J = 10.8, 8.1, 109.47, 81.58, 75.16, 496.2600 7.0 Hz, 1H), 4.20 (t, J = 8.7 Hz, 56.08, 51.58, 42.02, 1H), 3.92 (s, 3H), 37.25, 36.82, 33.66, 2.45-2.31 (m, 1H), 1.97-1.35 (m, 33.63, 31.76, 25.04, 14H), 1.31 (d, J = 6.5 Hz, 3H), 19.03, 18.40 1.22-1.06 (m, 1H), 1.10-0.89 (m, 2H) F28 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.06 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.43 (d, J = 8.1 Hz, 176.16, 172.19, 2941, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 168.64, 157.98, 1731, calcd for 1H), 7.07-6.99 (m, 2H), 155.37, 148.76, 1512 C₃₀H₃₈N₂O₈, 6.89-6.77 (m, 3H), 5.12-4.97 (m, 140.50, 131.86, 554.2628; 2H), 4.60 (ddd, J = 11.0, 8.1, 130.38, 129.64, found, 7.0 Hz, 1H), 3.94 (s, 3H), 113.87, 109.48, 75.53, 554.2634 3.79 (s, 3H), 2.82-2.71 (m, 1H), 73.53, 56.08, 55.24, 2.64 (dd, J = 13.6, 3.8 Hz, 51.43, 44.17, 44.04, 1H), 2.38-2.27 (m, 2H), 35.75, 33.45, 30.10, 2.02-1.56 (m, 13H), 1.30 (d, J = 5.8 Hz, 30.03, 26.72, 25.73, 3H), 1.02-0.92 (m, 18.66, 17.57 1H) F29 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹⁹F NMR (CDCl₃) δ −89.56 Film) (m/z) 1H), 8.45 (d, J = 8.2 Hz, 2938, ([M]⁺) 1H), 7.97 (d, J = 5.2 Hz, 1741, calcd for 1H), 7.12-7.03 (m, 4H), 1649, C₂₈H₃₆F₂N₂O₇, 6.86 (d, J = 5.1 Hz, 1H), 6.83 (d, J = 2.0 Hz, 1528, 550.2491; 3H), 4.92 (dq, J = 9.2, 1448, found, 6.4 Hz, 1H), 4.56 (ddd, J = 10.9, 1264 550.2503 8.2, 7.0 Hz, 1H), 3.93 (s, 3H), 3.79 (s, 3H), 3.18 (t, J = 9.0 Hz, 1H), 3.00 (dd, J = 13.4, 3.5 Hz, 1H), 2.39-2.11 (m, 4H), 1.87-1.74 (m, 1H), 1.67 (t, J = 18.7 Hz, 3H), 1.62-1.49 (m, 1H), 1.45 (s, 3H), 1.38-1.17 (m, 2H), 0.96-0.82 (m, 1H) F30 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.9 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.44 (d, J = 8.2 Hz, 172.13, 168.62, 3366, ([M]⁺) 1H), 7.98 (dd, J = 5.2, 1.1 Hz, 157.86, 155.33, 2938, calcd for 1H), 7.09 (d, J = 8.4 Hz, 148.71, 140.51, 1741, C₂₈H₃₆N₂O₇, 1H), 6.92-6.74 (m, 2H), 132.60, 129.73, 1649, 512.2523; 5.03-4.85 (m, 1H), 4.56 (dt, J = 10.7, 113.80, 109.45, 99.99, 1528, found, 7.6 Hz, 1H), 3.94 (s, 3H), 83.78, 78.76, 75.52, 1511, 512.2536 3.79 (s, 3H), 3.58 (dd, J = 9.7, 56.07, 55.24, 51.44, 1243 7.0 Hz, 1H), 3.45 (dd, J = 9.7 46.11, 35.94, 33.63, 6.8 Hz, 1H), 3.17 (t, J = 9.0 Hz, 26.56, 18.73, 18.12, 1H), 3.09 (d, J = 13.6 Hz, 11.18, 3.16, 3.02 1H), 2.34-2.20 (m, 2H), 1.90-1.78 (m, 1H), 1.60-1.51 (m, 5H), 1.47 (d, J = 6.4 Hz, 3H), 1.35-1.18 (m, 1H), 1.18-1.07 (m, 1H), 0.93-0.82 (m, 1H), 0.70-0.40 (m, 2H), 0.34-0.22 (m, 2H) F31 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.49 (d, J = 8.2 Hz, 1H), 172.23, 168.62, 3367, ([M]⁺) 7.99 (d, J = 5.2 Hz, 1H), 155.34, 148.71, 2942, calcd for 6.86 (d, J = 5.2 Hz, 1H), 4.91 (dq, J = 9.3, 140.52, 130.46, 2868, C₂₆H₃₈N₂O₆, 6.4 Hz, 1H), 4.55 (ddd, 109.45, 84.31, 78.54, 1740, 474.2730; J = 10.7, 8.2, 6.9 Hz, 1H), 75.64, 56.07, 51.54, 1649, found, 3.94 (s, 3H), 3.50 (dd J = 9.6, 7.0 Hz, 42.29, 37.27, 36.90, 1528, 474.2743 1H), 3.36 (dd, J = 9.6, 6.8 Hz, 33.97, 33.67, 31.85, 1057 1H), 3.01 (t, J = 8.9 Hz, 27.52, 25.11, 25.08, 1H), 2.34 (dt, J = 13.3, 6.8 Hz, 18.93, 18.11, 11.14, 1H), 1.92-1.45 (m, 13H), 3.14, 2.95 1.43 (d, J = 6.4 Hz, 3H), 1.40-1.29 (m, 1H), 1.16-0.94 (m, 4H), 0.59-0.49 (m, 2H), 0.21 (dt, J = 6.0, 4.5 Hz, 2H) F32 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.15, 168.61, 3368, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 157.83, 155.32, 2939, calcd for 7.08 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 5.3 Hz, 148.69, 140.51, 1742, C₂₈H₃₈N₂O₇, 1H), 6.83 (d, J = 8.6 Hz, 132.72, 130.39, 1650, 514.2679; 2H), 4.93 (dq, J = 9.3, 6.4 Hz, 129.70, 113.77, 1529, found, 1H), 4.56 (ddd, J = 10.9, 109.44, 83.66, 80.65, 1511, 514.2659 8.2, 7.0 Hz, 1H), 3.93 (s, 3H), 75.56, 56.06, 55.23, 1244 3.79 (s, 3H), 3.56 (dd, J = 8.4, 51.44, 46.25, 35.76, 6.2 Hz, 1H), 3.34 (dd, J = 8.4, 33.62, 29.26, 26.50, 6.5 Hz, 1H), 3.15 (t, J = 9.0 Hz, 19.54, 19.49, 18.77, 1H), 3.05 (dd, J = 13.3, 18.18 3.2 Hz, 1H), 2.37-2.22 (m, 2H), 1.91 (dq, J = 13.2, 6.6 Hz, 1H), 1.80 (ddq, J = 12.0, 7.5, 4.3, 3.6 Hz, 1H), 1.66-1.54 (m, 3H), 1.53-1.38 (m, 1H), 1.46 (d, J = 6.4 Hz, 3H), 0.97 (dd, J = 6.7, 4.8 Hz, 6H), 0.94-0.81 (m, 1H) F33 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.15, 168.61, 3369, ([M]⁺) 7.98 (d, J = 5.1 Hz, 1H), 157.83, 155.32, 2938, calcd for 7.08 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 5.3 Hz, 148.70, 140.51, 2877, C₂₇H₃₆N₂O₇, 1H), 6.83 (d, J = 8.6 Hz, 132.67, 130.40, 1742, 500.2523; 2H), 4.93 (dq, J = 9.2, 6.4 Hz, 129.71, 113.77, 1650, found, 1H), 4.56 (ddd, J = 11.0, 109.44, 83.95, 75.62, 1529, 500.2522 8.3, 7.0 Hz, 1H), 3.94 (s, 3H), 75.53, 56.07, 55.23, 1512, 3.79 (s, 3H), 3.73 (dt, J = 8.6, 51.45, 46.12, 35.86, 1244 6.5 Hz, 1H), 3.52 (dt, J = 8.7, 33.63, 26.53, 23.59, 6.7 Hz, 1H), 3.16 (t, J = 9.0 Hz, 18.75, 18.12, 10.75 1H), 3.05 (dd, J = 13.3, 3.3 Hz, 1H), 2.37-2.24 (m, 2H), 1.80 (ddt, J = 12.1, 8.3, 3.9 Hz, 1H), 1.64 (dt, J = 14.0, 7.0 Hz, 3H), 1.64-1.54 (m, 1H), 1.54-1.41 (m, 1H), 1.47 (d, J = 6.4 Hz, 3H), 1.32-1.19 (m, 1H), 0.99 (d, J = 7.3 Hz, 3H), 0.94-0.79 (m, 1H) F34 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.7 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.47 (d, J = 8.2 Hz, 172.16, 168.62, 3367, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.32, 154.60, 2941, calcd for 1H), 7.31 (dd, J = 2.0, 0.8 Hz, 148.70, 141.04, 2874, C₂₅H₃₄N₂O₇, 1H), 6.89-6.83 (m, 1H), 140.52, 130.40, 1741, 474.2366; 6.28 (dd, J = 3.1, 1.9 Hz, 1H), 110.11, 109.45, 1649, found, 6.02 (d, J = 3.1 Hz, 1H), 4.94 (dq, J = 9.2, 106.08, 83.43, 80.26, 1528, 474.2394 6.4 Hz, 1H), 4.56 (ddd, 75.45, 56.06, 51.48, 1056 J = 10.9, 8.2, 6.9 Hz, 1H), 43.15, 33.52, 29.35, 3.94 (s, 3H), 3.50 (dd, J = 8.4, 6.5 Hz, 29.21, 27.93, 19.48, 1H), 3.31 (dd, J = 8.4, 6.3 Hz, 19.46, 18.84, 18.18 1H), 3.15 (t, J = 9.0 Hz, 1H), 3.01 (dd, J = 14.6, 3.5 Hz, 1H), 2.52 (dd, J = 14.6, 11.2 Hz, 1H), 2.35-2.22 (m, 1H), 1.96 (ddt, J = 14.8, 6.8, 3.5 Hz, 1H), 1.86 (dq, J = 13.2, 6.6 Hz, 1H), 1.71-1.49 (m, 3H), 1.45 (d, J = 6.4 Hz, 3H), 1.39-1.28 (m, 1H), 1.07-0.95 (m, 1H), 0.94 (d, J = 6.7 Hz, 6H) F35 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.48 (d, J = 8.1 Hz, 1H), 176.47, 172.25, 3388, ([M]⁺) 7.99 (d, J = 5.2 Hz, 1H), 168.63, 155.35, 2957, calcd for 6.87 (d, J = 5.2 Hz, 1H), 5.03 (dq, J = 9.5, 148.74, 140.50, 1730, C₂₆H₃₈N₂O₇, 6.4 Hz, 1H), 4.86 (t, J = 9.1 Hz, 130.39, 109.47, 73.59, 1649, 490.2679; 1H), 4.59 (ddd, J = 10.9, 56.07, 51.49, 40.61, 1525, found, 8.1, 7.0 Hz, 1H), 3.94 (s, 36.99, 36.50, 34.29, 1146 490.2689 3H), 2.58 (hept, J = 7.0 Hz, 33.68, 33.47, 31.85, 1H), 2.44-2.32 (m, 1H), 27.24, 25.03, 25.01 1.93-0.87 (m, 26H) 19.11, 18.95, 18.78, 17.50 F36 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.51 (d, J = 8.1 Hz, 1H), 172.25, 168.61, 3323, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.29, 148.67, 2941, calcd for 6.86 (d, J = 5.2 Hz, 1H), 4.89 (dq, J = 9.3, 140.50, 130.40, 2869, C₂₅H₃₈N₂O₆, 6.4 Hz, 1H), 4.55 (ddd, 109.44, 84.49, 75.64, 1736, 462.2730; J = 10.8, 8.3, 7.0 Hz, 1H), 75.34, 56.04, 51.53, 1650, found, 3.94 (s, 3H), 3.64 (dt, J = 8.6, 6.5 Hz, 42.19, 37.25, 36.80, 1532, 462.2738 1H), 3.44 (dt, J = 8.7, 6.8 Hz, 33.93, 33.60, 31.77, 1190 1H), 3.01 (t, J = 8.9 Hz, 27.51, 25.09, 25.07, 1H), 2.34 (dt, J = 13.4, 6.9 Hz, 23.53, 18.94, 18.10, 1H), 1.91-1.22 (m, 18H), 10.73 1.18-0.98 (m, 4H), 0.94 (t, J = 7.4 Hz, 3H) F37 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.51 (d, J = 8.2 Hz, 172.25, 168.61, 3342, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.29, 148.67, 2946, calcd for 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.50, 130.41, 2869, C₂₆H₄₀N₂O₆, 4.89 (dq, J = 9.4, 6.5 Hz, 1H), 109.44, 84.21, 80.40, 1738, 476.2886; 4.55 (ddd, J = 10.8, 8.2, 7.0 Hz, 75.70, 56.04, 51.54, 1648, found, 1H), 3.94 (s, 3H), 42.21, 37.21, 36.70, 1189, 476.2890 3.81-3.60 (m, 1H), 3.47 (dd, J = 8.4, 33.96, 33.60, 31.72, 1054 6.0 Hz, 1H), 3.25 (dd, J = 8.4, 29.19, 27.50, 25.08, 6.7 Hz, 1H), 2.99 (t, J = 8.8 Hz, 25.07, 19.54, 19.43, 1H), 2.34 (dt, J = 13.0, 6.6 Hz, 18.96, 18.15 1H), 1.93-1.21 (m, 16H), 1.20-0.84 (m, 10H) F38 160-163 — HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J = 8.1 Hz, 1H), 172.23, 168.64, [M + H]⁺ 8.00 (d, J = 5.2 Hz, 1H), 159.64, 155.34, calcd for 7.34-7.23 (m, 2H), 6.96 (dd, J = 7.9, 148.71, 140.54, C₂₃H₂₉N₂O₆, 3.7 Hz, 3H), 6.87 (d, J = 5.2 Hz, 130.39, 129.61, 429.2020; 1H), 5.12 (dq, J = 9.1, 121.04, 115.48, found, 6.4 Hz, 1H), 4.61 (dt, J = 11.0, 109.47, 82.22, 74.96, 429.2028 7.1 Hz, 1H), 4.18 (t, J = 8.8 Hz, 56.08, 51.60, 37.65, 1H), 3.94 (s, 3H), 2.40 (dt, 33.55, 32.29, 19.19, J = 13.3, 6.7 Hz, 1H), 18.31, 17.75 1.99-1.87 (m, 1H), 1.73 (ddt, J = 19.3, 12.4, 6.2 Hz, 3H), 1.52-1.39 (m, 1H), 1.33 (d, J = 6.5 Hz, 3H), 1.28 (dt, J = 10.5, 5.2 Hz, 1H), 1.02 (d, J = 6.9 Hz, 3H) F39 129-130 — HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.50 (d, J = 8.1 Hz, 1H), 172.27, 168.64, [M + H]⁺ 7.99 (d, J = 5.2 Hz, 1H), 155.33, 148.71, calcd for 7.35 (d, J = 3.8 Hz, 5H), 6.86 (d, J = 5.2 Hz, 140.53, 138.00, C₂₄H₃₁N₂O₆, 1H), 4.97 (dq, J = 9.1, 130.43, 128.48, 443.2177; 6.4 Hz, 1H), 4.72 (d, J = 10.8 Hz, 127.84, 127.73, found, 1H), 4.64-4.54 (m, 109.46, 85.25, 75.60, 443.2171 2H), 3.94 (s, 3H), 3.24 (t, J = 8.9 Hz, 75.45, 56.07, 51.56, 1H), 2.36 (dt, J = 13.3, 37.94, 33.61, 32.24, 6.7 Hz, 1H), 1.84-1.55 (m, 19.07, 18.23, 17.79 4H), 1.49 (d, J = 6.4 Hz, 3H), 1.41 (dt, J = 13.3, 10.8 Hz, 1H), 1.22-1.16 (m, 1H), 1.08 (d, J = 6.8 Hz, 3H) F40 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 429.3 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.06, 168.65, ([M + H]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.36, 148.72, 7.30 (dd, J = 8.4, 6.3 Hz, 2H), 140.53, 140.45, 7.21 (td, J = 7.2, 6.7, 1.5 Hz, 3H), 130.37, 128.86, 6.86 (d, J = 5.3 Hz, 1H), 128.55, 126.17, 4.90 (dq, J = 9.3, 6.3 Hz, 1H), 109.48, 76.11, 74.90, 4.58 (ddd, J = 10.9, 8.2, 7.1 Hz, 56.08, 51.35, 47.48, 1H), 3.94 (s, 3H), 3.56 (td, J = 9.0, 37.78, 33.51, 26.97, 8.5, 2.7 Hz, 1H), 3.13 (dd, 18.89, 18.14 J = 13.5, 4.5 Hz, 1H), 2.48 (dd, J = 13.5, 10.5 Hz, 1H), 2.33 (dt, J = 14.0, 7.2 Hz, 1H), 1.85-1.73 (m, 2H), 1.72-1.51 (m, 3H), 1.44 (d, J = 6.3 Hz, 3H), 1.36-1.24 (m, 1H), 1.04-0.91 (m, 1H) F41 129-131 — ESIMS ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ m/z 499 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.16, 168.63, ([M + H]⁺) 8.03-7.89 (m, 1H), 155.32, 148.70, 7.12-7.02 (m, 4H), 6.85 (d, J = 5.2 Hz, 140.52, 137.60, 1H), 4.93 (dq, J = 9.2, 6.4 Hz, 135.37, 130.40, 1H), 4.62-4.50 (m, 1H), 129.06, 128.72, 3.92 (s, 3H), 3.56 (dd, J = 8.4, 109.46, 83.67, 80.66, 6.2 Hz, 1H), 3.34 (dd, J = 8.4, 75.57, 56.06, 51.46, 6.5 Hz, 1H), 3.15 (t, J = 9.0 Hz, 46.15, 36.24, 33.61, 1H), 3.07 (dd, J = 13.3, 29.28, 26.50, 21.04, 3.2 Hz, 1H), 2.38-2.24 (m, 19.56, 19.50, 18.77, 5H), 1.97-1.78 (m, 2H), 18.19 1.68-1.54 (m, 2H), 1.54-1.40 (m, 4H), 1.25 (dtd, J = 13.2, 10.6, 2.2 Hz, 1H), 0.97 (d, J = 6.7 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 0.92-0.81 (m, 1H) F42 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 497 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.13, 168.62, ([M + H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 155.32, 148.70, 7.14-7.03 (m, 4H), 6.85 (d, J = 5.2 Hz, 140.52, 137.47, 1H), 4.94 (dq, J = 9.2, 6.4 Hz, 135.39, 130.38, 1H), 4.56 (ddd, J = 10.9, 129.07, 128.73, 8.3, 7.0 Hz, 1H), 3.93 (s, 3H), 109.46, 83.75, 78.75, 3.58 (dd, J = 9.7, 7.0 Hz, 1H), 75.51, 56.06, 51.43, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 46.01, 36.39, 33.60, 3.18 (t, J = 9.0 Hz, 1H), 26.54, 21.03, 18.71, 3.11 (dd, J = 13.2, 3.3 Hz, 1H), 18.11, 11.18, 3.16, 2.37-2.23 (m, 5H), 3.02 1.93-1.82 (m, 1H), 1.66-1.53 (m, 2H), 1.53-1.41 (m, 4H), 1.31-1.20 (m, 1H), 1.18-1.08 (m, 1H), 0.93-0.83 (m, 1H), 0.62-0.55 (m, 2H), 0.29-0.22 (m, 2H) F43 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 12.19-11.98 (m, 1H), 8.50 (d, J = 8.2 Hz, 172.18, 168.63, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.34, 148.71, calcd for 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.54, 130.40, C₂₂H₃₄N₂O₆, 4.91 (dt, J = 9.1, 6.4 Hz, 1H), 109.46, 83.79, 82.16, 441.2395; 4.63-4.52 (m, 2H), 80.24, 75.52, 56.08, found, 4.52-4.39 (m, 1H), 3.94 (s, 3H), 51.52, 39.76, 33.48, 441.2411 3.45 (dd, J = 8.3, 6.6 Hz, 1H), 31.59, 31.39, 29.17, 3.26 (dd, J = 8.4, 6.4 Hz, 1H), 28.64, 19.45, 19.41, 3.08 (t, J = 8.6 Hz, 1H), 19.12, 18.14 2.35 (dt, J = 13.3, 6.6 Hz, 1H), 2.16-1.95 (m, 1H), 1.92-1.79 (m, 1H), 1.79-1.60 (m, 4H), 1.60-1.52 (m, 1H), 1.43 (d, J = 6.4 Hz, 3H), 1.42-1.34 (m, 1H), 1.11 (dd, J = 14.9, 5.2 Hz, 1H), 0.92 (dd, J = 6.7, 0.7 Hz, 6H) F44 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 12.17-11.97 (m, 1H), 8.52 (d, J = 8.1 Hz, 172.16, 168.66, [M + H]⁺ 1H), 8.00 (d, J = 5.2 Hz, 159.31, 158.75, calcd for 1H), 7.37-7.27 (m, 2H), 155.35, 148.72, C₃₀H₃₅N₂O₇, 7.25-7.20 (m, 2H), 7.03-6.78 (m, 140.56, 130.37, 535.2439; 7H), 5.13 (dt, J = 9.1, 6.5 Hz 129.71, 129.40, found, 1H), 4.69-4.56 (m, 1H), 121.23, 120.64, 535.2459 4.30 (t, J = 8.7 Hz, 1H), 3.95 (d, J = 7.6 Hz, 115.40, 114.44, 5H), 2.41 (dt, J = 12.7, 109.49, 81.08, 75.04, 6.5 Hz, 1H), 2.17-2.02 (m, 66.00, 56.08, 51.56, 2H), 2.02-1.86 (m, 1H), 40.19, 37.62, 33.51, 1.86-1.64 (m, 3H), 1.45 (q, J = 11.1 Hz, 30.50, 28.39, 19.25, 1H), 1.34 (d, J = 6.5 Hz, 18.35 3H), 1.31-1.20 (m, 1H) F45 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J = 8.1 Hz, 1H), 171.49, 167.99, [M + H]⁺ 8.00 (d, J = 5.2 Hz, 1H), 158.77, 154.70, calcd for 7.33-7.27 (m, 2H), 6.94 (dd, J = 7.9, 148.07, 139.89, C₂₅H₃₃N₂O₇, 5.5 Hz, 3H), 6.87 (d, J = 5.2 Hz, 129.73, 128.98, 473.2282; 1H), 5.19-5.01 (m, 120.45, 114.72, found, 1H), 4.61 (dt, J = 10.9, 7.1 Hz, 108.83, 80.40, 74.44, 473.2297 1H), 4.25 (t, J = 8.8 Hz, 1H), 70.13, 57.80, 55.42, 3.95 (s, 3H), 3.38 (t, J = 6.4 Hz, 50.89, 39.47, 32.90, 2H), 3.27 (s, 3H), 2.40 (dt, 29.89, 27.44, 18.46, J = 12.8, 6.5 Hz, 1H), 17.70 2.02-1.80 (m, 3H), 1.80-1.60 (m, 2H), 1.56-1.37 (m, 2H), 1.31 (d, J = 6.5 Hz, 3H), 1.19 (dd, J = 14.7, 7.8 Hz, 1H) F46 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J = 8.1 Hz, 172.14, 168.61, ([M + Na]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.28, 148.65, calcd for 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.50, 130.35, C₂₃H₃₆N₂O₆SNa, 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 109.45, 83.85, 80.36, 491.2186; 4.64-4.50 (m, 1H), 3.94 (s, 75.55, 56.03, 51.48, found, 3H), 3.46 (dd, J = 8.4, 6.5 Hz, 42.19, 33.42, 32.10, 491.2199 1H), 3.28 (dd, J = 8.4, 6.4 Hz, 29.90, 29.17, 29.02, 1H), 3.05 (t, J = 8.8 Hz, 1H), 27.74, 25.25, 19.45, 2.59 (ddd, J = 12.9, 9.6, 4.6 Hz, 18.91, 18.12, 15.33 1H), 2.44 (ddd, J = 12.7, 9.0, 7.3 Hz, 1H), 2.35 (dt, J = 12.9, 6.7 Hz, 1H), 2.10 (s, 3H), 1.95 (dddd, J = 12.5, 9.8, 6.0, 3.0 Hz, 1H), 1.85 (dt, J = 13.2, 6.6 Hz, 1H), 1.80-1.58 (m, 4H), 1.58-1.46 (m, 2H), 1.43 (d, J = 6.4 Hz, 3H), 1.06 (ddd, J = 11.4, 6.3, 3.2 Hz, 1H), 0.93 (dd, J = 6.7, 0.9 Hz, 6H) F47 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.50 (d, J = 8.1 Hz, 172.22, 168.61, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.33, 148.70, calcd for 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.52, 130.42, C₂₃H₃₆O₇Na, 4.90 (dq, J = 9.1, 6.4 Hz, 1H), 109.44, 83.97, 80.37, 475.2415; 4.56 (ddd, J = 10.8, 8.1, 7.0 Hz, 75.65, 71.25, 58.52, found, 1H), 3.94 (s, 3H), 3.42 (q, 56.07, 51.53, 40.24, 475.2836 J = 6.7, 6.3 Hz, 3H), 3.33 (s, 33.56, 30.39, 29.17, 3H), 3.32-3.26 (m, 1H), 28.30, 19.51, 19.42, 3.05 (t, J = 8.8 Hz, 1H), 2.35 (dt, J = 13.2, 19.04, 18.16 6.5 Hz, 1H), 2.05-1.91 (m, 1H), 1.91-1.78 (m, 1H), 1.78-1.62 (m, 3H), 1.59-1.45 (m, 2H), 1.43 (d, J = 6.4 Hz, 3H), 1.40-1.32 (m, 1H), 1.11-1.02 (m, 1H), 0.92 (dd, J = 6.7, 2.7 Hz, 6H) F48 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.50 (d, J = 8.1 Hz, 172.26, 168.61, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.32, 148.69, calcd for 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.52, 130.44, C₂₂H₃₅O₆N₂, 4.90 (dq, J = 9.2, 6.4 Hz, 1H), 109.43, 84.18, 80.43, 423.2490; 4.62-4.48 (m, 1H), 3.94 (s, 75.72, 56.07, 51.53, found, 3H), 3.43 (dd, J = 8.4, 6.6 Hz, 45.18, 33.64, 29.18, 423.2500 1H), 3.27 (dd, J = 8.4, 6.4 Hz, 27.05, 23.25, 19.50, 1H), 3.02 (t, J = 8.9 Hz, 1H), 19.45, 18.74, 18.19, 2.34 (dt, J = 13.1, 6.9 Hz, 1H), 11.96 1.92-1.80 (m, 1H), 1.73 (dtt, J = 15.4, 7.5, 3.5 Hz, 2H), 1.61 (dd, J = 14.8, 7.1 Hz, 1H), 1.55-1.45 (m, 1H), 1.42 (d, J = 6.4 Hz, 4H), 1.40-1.32 (m, 1H), 1.28-1.17 (m, 1H), 1.06-0.96 (m, 1H), 0.94-0.88 (m, 9H) F49 62-66 — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 519 1H), 8.48 (d, J = 8.2 Hz, 1H), 172.06, 168.59, ([M + H]⁺) 7.98 (d, J = 5.1 Hz, 1H), 159.58, 155.27, 7.37-7.28 (m, 2H), 7.12-6.93 (m, 148.66, 140.47, 7H), 6.86 (d, J = 5.2 Hz, 1H), 136.92, 135.38, 5.14 (dq, J = 9.2, 6.4 Hz, 1H), 130.28, 129.63, 4.62 (dt, J = 10.9, 7.4 Hz, 1H), 128.98, 128.59, 4.35 (t, J = 8.9 Hz, 1H), 121.16, 115.48, 3.93 (s, 3H), 2.99 (dd, J = 13.3, 3.2 Hz, 109.43, 81.02, 74.89, 1H), 2.42-2.26 (m, 5H), 55.99, 51.43, 45.59, 2.16-2.04 (m, 1H), 36.34, 33.47, 26.57, 1.79-1.52 (m, 3H), 1.41-1.23 (m, 20.95, 18.78, 18.33 4H), 1.08-0.98 (m, 1H) F50 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 12.27-11.86 (m, 1H), 8.53 (d, J = 8.1 Hz, 172.08, 168.68, [M + H]⁺ 1H), 8.00 (d, J = 5.2 Hz, 159.15, 155.37, calcd for 1H), 7.37-7.27 (m, 2H), 148.74, 140.58, C₂₄H₃₀O₆BrN₂, 7.04-6.92 (m, 3H), 6.88 (d, J = 5.2 Hz, 130.35, 129.77, 521.1282; 1H), 5.13 (dq, J = 9.1, 6.5 Hz, 121.39, 115.38, found, 1H), 4.62 (ddd, J = 10.9, 109.52, 80.87, 74.94, 521.1283 8.0, 6.8 Hz, 1H), 4.25 (t, J = 8.7 Hz, 56.09, 51.57, 41.28, 1H), 3.95 (s, 3H), 34.14, 33.37, 31.47, 3.46 (ddd, J = 10.0, 7.3, 5.0 Hz, 28.22, 19.16, 18.29 1H), 3.35 (ddd, J = 10.0, 8.3, 6.9 Hz, 1H), 2.50-2.33 (m, 1H), 2.10 (m, 2H), 1.94-1.78 (m, 2H), 1.73 (dt, J = 15.8, 8.0 Hz, 2H), 1.54-1.40 (m, 1H), 1.33 (d, J = 6.5 Hz, 3H), 1.30-1.18 (m, 1H) 51 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J = 8.1 Hz, 172.20, 168.65, [M + H]⁺ 1H), 8.00 (d, J = 5.2 Hz, 159.64, 155.35, calcd for 1H), 7.34-7.27 (m, 2H), 148.73, 140.54, C₂₄H₃₁O₆N₂, 7.01-6.91 (m, 3H), 6.87 (d, J = 5.2 Hz, 130.41, 129.61, 443.2177; 1H), 5.10 (dq, J = 9.1, 6.5 Hz, 121.00, 115.40, found, 1H), 4.61 (ddd, J = 10.8, 109.48, 81.38, 75.11, 443.2186 8.0, 7.1 Hz, 1H), 4.23 (t, J = 8.8 Hz, 56.08, 51.56, 44.97, 1H), 3.94 (s, 3H), 33.61, 26.99, 23.52, 2.47-2.33 (m, 1H), 1.95-1.83 (m, 18.80, 18.39, 11.87 1H), 1.78-1.59 (m, 4H), 1.50-1.38 (m, 1H), 1.31 (d, J = 6.5 Hz, 3H), 1.28-1.21 (m, 1H), 1.21-1.10 (m, 1H), 0.88 (t, J = 7.3 Hz, 3H) F52 68-72 — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 555 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.03, 168.60, ([M + H]⁺) 7.98 (d, J = 5.2 Hz, 1H), 161.32 (dd, J = 247.2, 12.6 Hz), 7.42-7.28 (m, 5H), 7.09 (td, J = 8.7, 161.06 (dd, J = 247.1, 6.6 Hz, 1H), 6.86 (d, J = 5.3 Hz, 11.6 Hz), 1H), 6.83-6.72 (m, 155.28, 148.66, 2H), 5.01 (dq, J = 9.2, 6.4 Hz, 140.48, 137.70, 1H), 4.82 (d, J = 10.9 Hz, 1H), 131.77-131.21 (m), 130.30, 4.64 (d, J = 10.9 Hz, 1H), 128.48, 127.88, 4.59 (dt, J = 10.9, 7.4 Hz, 1H), 127.60, 123.02 (dd, J = 16.0, 3.93 (s, 3H), 3.42 (t, J = 9.0 Hz, 3.9 Hz), 1H), 3.10-2.99 (m, 1H), 111.04 (dd, J = 20.9, 3.6 Hz), 2.51 (dd, J = 13.5, 11.5 Hz, 1H), 109.43, 2.32 (dtd, J = 13.2, 6.6, 2.0 Hz, 104.17-103.09 (m), 83.83, 1H), 1.95 (ddq, J = 12.0, 7.8, 75.34, 75.17, 56.00, 3.8 Hz, 1H), 1.74-1.40 (m, 51.38, 44.42, 33.44, 6H), 1.34-1.22 (m, 1H), 29.25, 27.07, 18.77, 1.02-0.90 (m, 1H) 18.20 ¹⁹F NMR (CDCl₃) δ −113.21 (d, J = 6.7 Hz), −113.59 (d, J = 6.8 Hz) F53 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.06 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.54 (d, J = 8.1 Hz, 172.08, 168.69, [M + H]⁺ 1H), 8.03 (d, J = 5.2 Hz, 158.89, 155.37, calcd for 1H), 7.42-7.30 (m, 2H), 148.74, 140.59, C₂₄H₂₉O₆N₂F₂, 7.05-6.99 (m, 1H), 6.99-6.94 (m, 130.32, 129.86, 479.1988; 2H), 6.90 (d, J = 5.1 Hz, 1H), 121.62, 116.72 (t, J = 239 hz), found, 6.09-5.68 (m, 1H), 5.15 (dq, 115.25, 479.1989 J = 9.2, 6.5 Hz, 1H), 109.53, 80.51, 74.76, 4.65 (ddd, J = 11.0, 8.1, 6.9 Hz, 56.09, 51.54, 35.73 (t, 1H), 4.27 (t, J = 8.7 Hz, 1H), J = 21 Hz), 33.31, 3.97 (s, 3H), 2.45 (dt, J = 13.2, 29.34, 19.25, 18.27 6.7 Hz, 1H), 2.12 (dt, J = 8.7, 3.7 Hz, 1H), 2.04 (ddt, J = 14.5, 9.1, 4.6 Hz, 1H), 1.88 (dddd, J = 22.5, 14.7, 11.4, 7.1 Hz, 3H), 1.77-1.65 (m, 1H), 1.48 (q, J = 11.1 Hz, 1H), 1.35 (d, J = 6.5 Hz, 3H), 1.33-1.25 (m, 1H) F54 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.49 (d, J = 8.1 Hz, 172.18, 168.62, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.32, 148.70, calcd for 1H), 6.86 (d, J = 5.1 Hz, 1H), 140.52, 130.41, C₂₆H₃₉O₇N₂, 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 109.44, 83.96, 78.39, 491.2752; 4.66-4.47 (m, 1H), 3.94 (s, 75.59, 75.48, 69.09, found, 3H), 3.55-3.37 (m, 4H), 56.07, 51.48, 40.49, 491.2758 3.36-3.17 (m, 2H), 3.09 (t, J = 8.9 Hz, 33.58, 30.66, 28.15, 1H), 2.35 (dt, J = 13.3, 6.6 Hz, 18.97, 18.10, 11.09, 1H), 2.08-1.93 (m, 1H), 10.66, 3.18, 3.02, 2.95, 1.70 (tq, J = 13.2, 7.3, 5.3 Hz, 2.90 3H), 1.60-1.47 (m, 2H), 1.44 (d, J = 6.5 Hz, 3H), 1.42-1.31 (m, 1H), 1.17-0.94 (m, 3H), 0.54 (dddd, J = 10.0, 8.0, 4.1, 2.8 Hz, 4H), 0.32-0.13 (m, 4H) 55 66-70 — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 553 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.04, 168.57, ([M + H]⁺) 8.00-7.93 (m, 1H), 7.10 (d, J = 7.8 Hz, 155.26, 148.64, 2H), 7.04 (d, J = 8.0 Hz, 140.46, 137.13, 2H), 6.85 (d, J = 5.2 Hz, 135.46, 130.28, 1H), 4.92 (dq, J = 9.2, 6.4 Hz, 129.05, 128.57, 1H), 4.61-4.50 (m, 1H), 131.35-122.86 (m), 109.41, 3.92 (s, 3H), 3.80 (dt, J = 8.9, 6.1 Hz, 84.15, 75.08, 71.62, 1H), 3.61 (dt, J = 8.8, 6.2 Hz, 55.98, 51.37, 45.75, 1H), 3.18 (t, J = 9.0 Hz, 36.42, 33.46, 30.71 (q, 1H), 2.97 (dd, J = 13.3, 3.5 Hz, J = 29.1 Hz) 26.60, 1H), 2.41-2.13 (m, 7H), 23.01 (q, J = 3.1 Hz), 1.91-1.76 (m, 3H), 20.93, 18.69, 18.04 1.69-1.40 (m, 6H), 1.33-1.20 (m, ¹⁹F NMR (CDCl₃) δ −66.33 1H), 0.93-0.82 (m, 1H) F56 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 583 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.04, 168.58, ([M + H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 162.89-159.93 (m) 7.32-7.07 (m, 6H), 6.88-6.74 (m, 161.08 (dd J = 247.0, 11.6 Hz), 3H), 4.94 (dq, J = 9.2, 6.4 Hz, 155.27, 148.65 1H), 4.56 (dt, J = 10.9, 7.5 Hz, 141.66, 140.46, 1H), 3.92 (s, 3H), 3.79 (dt, J = 8.8, 131.49 (dd, J = 9.4, 6.5 Hz), 6.3 Hz, 1H), 3.58 (dt, J = 8.9, 130.31, 128.32, 6.5 Hz, 1H), 3.19 (t, J = 9.0 Hz, 128.27, 125.83, 1H), 2.99 (d, J = 13.2 Hz, 123.13 (dd, J = 15.9, 3.7 Hz), 1H), 2.74 (td, J = 7.5, 3.7 Hz, 111.02 (dd, J = 20.9, 2H), 2.48 (dd, J = 13.6, 3.7 Hz), 109.42, 11.5 Hz, 1H), 2.31 (dt, J = 12.7, 104.28-102.96 (m), 6.7 Hz, 1H), 83.96, 75.25, 72.90, 2.03-1.80 (m, 3H), 1.72-1.37 (m, 6H), 56.00, 51.36, 44.44, 1.34-1.20 (m, 1H), 33.45, 32.35, 31.88, 0.99-0.86 (m, 1H) 29.29, 27.04, 18.72, 18.07 ¹⁹F NMR (CDCl₃) δ −113.26 (d, J = 7.1 Hz), −113.60 (d, J = 6.9 Hz) F57 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.49 (d, J = 8.0 Hz, 1H), 172.15, 168.63, [M + H]⁺ 7.99 (d, J = 5.2 Hz, 1H), 158.82, 155.32, calcd for 7.37-7.27 (m, 2H), 6.99-6.80 (m, 148.70, 140.53, C₂₈H₃₇O₇N₂, 4H), 5.06-4.87 (m, 1H), 130.39, 129.43, 513.2595; 4.57 (dt, J = 10.8, 7.2 Hz, 1H), 120.62, 114.46, found, 4.09-3.98 (m, 2H), 3.94 (s, 3H), 109.45, 83.88, 78.27, 513.2605 3.57-3.35 (m, 2H), 3.15 (t, J = 8.9 Hz, 75.52, 66.14, 56.07, 1H), 2.35 (dt, J = 13.1, 51.47, 40.30, 33.54, 6.6 Hz, 1H), 2.21 (dq, J = 10.4, 30.31, 28.11, 19.03, 3.8 Hz, 1H), 1.81 (dd, 18.11, 11.08, 3.16, J = 11.2, 5.8 Hz, 2H), 2.94 1.79-1.66 (m, 2H), 1.61 (d, J = 10.7 Hz, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.44-1.33 (m, 1H), 1.08 (dq, J = 12.4, 6.3, 5.4 Hz, 2H), 0.55 (dt, J = 8.0, 4.6 Hz, 2H), 0.21 (q, J = 5.1 Hz, 2H) F58 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.6 Hz, 13C NMR (151 MHz, (m/z) 1H), 8.58 (d, J = 7.7 Hz, CDCl₃) 173.09, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 168.55, 155.35, calcd for 1H), 6.87 (d, J = 5.1 Hz, 1H), 148.74, 140.54, C₁₈H₂₅O₆N₂, 5.02 (dq, J = 9.5, 6.3 Hz, 1H), 130.44, 109.46, 86.83, 365.1707; 4.52 (ddd, J = 12.0, 7.9, 5.2 Hz, 73.59, 67.75, 56.08, found, 1H), 3.94 (s, 3H), 52.94, 39.75, 36.06, 365.17012 3.82 (ddd, J = 8.6, 7.1, 3.4 Hz, 1H), 35.77, 32.40, 21.75, 3.71 (td, J = 8.9, 5.3 Hz, 1H), 18.39 3.44 (dd, J = 9.5, 6.3 Hz, 1H), 2.38 (dddd, J = 14.0, 11.4, 5.2, 1.9 Hz, 1H), 2.13-2.03 (m, 1H), 1.98 (ddt, J = 14.7, 8.1, 3.3 Hz, 1H), 1.94-1.86 (m, 1H), 1.84-1.72 (m, 1H), 1.71-1.60 (m, 1H), 1.56-1.48 (m, 2H), 1.47 (dd, J = 5.8, 2.1 Hz, 1H), 1.44 (d, J = 6.3 Hz, 3H) F59 69-72 — ESIMS ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ m/z 521 1H), 8.44 (d, J = 8.2 Hz, 1H), 172.03, 168.56, ([M + H]⁺) 7.95 (d, J = 5.1 Hz, 1H), 161.27 (dd, J = 246.8, 12.2 Hz), 7.11 (td, J = 8.5, 6.4 Hz, 1H), 162.42-159.71 (m), 155.25, 148.62, 6.84 (d, J = 5.2 Hz, 1H), 140.45, 131.50 (dd, J = 9.2, 6.82-6.71 (m, 2H), 4.91 (dq, J = 9.2, 6.6 Hz), 130.29, 6.4 Hz, 1H), 4.55 (dt, J = 10.9, 123.20 (dd, J = 16.2, 7.5 Hz, 1H), 3.91 (s, 3H), 3.7 Hz), 111.00 (dd, J = 20.9, 3.54 (dd, J = 8.4, 6.3 Hz, 1H), 3.7 Hz), 3.31 (dd, J = 8.4, 6.5 Hz, 1H), 109.40, 3.15 (t, J = 9.0 Hz, 1H), 103.99-103.17 (m), 83.45, 3.04-2.93 (m, 1H), 2.46 (dd, J = 13.5, 80.36, 75.37, 55.98, 11.6 Hz, 1H), 2.36-2.24 (m, 51.34, 44.65, 33.44, 1H), 1.94-1.77 (m, 2H), 29.16, 29.10, 26.96, 1.70-1.51 (m, 2H), 1.45 (d, J = 6.4 Hz, 19.40, 19.38, 18.70, 4H), 1.33-1.19 (m, 1H), 18.06 0.95 (dd, J = 6.7, 4.7 Hz, 7H) ¹⁹F NMR (CDCl₃) δ −113.36 (d, J = 6.4 Hz), −113.63 (d, J = 6.4 Hz) F60 93-97 — ESIMS ¹H NMR (CDCl₃) δ 12.03 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ m/z 559 1H), 8.43 (d, J = 8.1 Hz, 171.98, 168.58, [M + H]⁺ 1H), 7.95 (d, J = 5.2 Hz, 161.44 (dd, J = 246.7, 11.8 Hz) 1H), 7.60 (dd, J = 1.8, 0.9 Hz, 160.93 (dd, J = 247.6, 1H), 7.17 (dd, J = 3.5, 0.9 Hz, 11.8 Hz), 1H), 7.04 (td, J = 8.4, 6.4 Hz, 158.10, 155.25, 1H), 6.84 (d, J = 5.2 Hz, 1H), 148.63, 146.90, 6.75-6.65 (m, 2H), 6.51 (dd, 143.79, 140.44, J = 3.5, 1.7 Hz, 1H), 5.21 (t, J = 9.2 Hz, 131.51 (dd, J = 9.4, 6.5 Hz), 1H), 5.12 (dq, J = 9.5, 130.20, 122.32 (dd, J = 15.9, 6.2 Hz, 1H), 4.60 (dt, J = 10.9, 3.7 Hz), 7.5 Hz, 1H), 3.91 (s, 3H), 118.60, 111.94, 2.72 (dd, J = 13.9, 4.5 Hz, 110.89 (dd, J = 21.0, 3.6 Hz), 1H), 2.51 (dd, J = 13.9, 10.3 Hz, 109.43, 103.64 (t, J = 25.6 Hz), 1H), 2.36 (dtd, J = 13.3, 76.26, 73.31, 7.7, 6.7, 3.4 Hz, 1H), 55.97, 51.28, 42.53, 2.20-2.08 (m, 1H), 1.77-1.54 (m, 33.25, 29.99, 27.24, 3H), 1.40-1.25 (m, 4H), 18.61, 17.44 1.13-1.01 (m, 1H) ¹⁹F NMR (CDCl₃) δ −112.90 (d, J = 6.8 Hz), −113.48 (d, J = 6.7 Hz) F61 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.07 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.53 (d, J = 8.1 Hz, 1H), 172.22, 168.65, [2M + Na]⁺ 7.35-7.22 (m, 3H), 6.93 (dd, 159.29, 155.35, calcd for J = 7.4, 4.7 Hz, 3H), 6.87 (d, J = 5.2 Hz, 148.73, 140.56, C₄₈H₅₆N₄NaO₁₂, 1H), 5.79 (ddd, J = 17.2, 138.40, 130.37, 903.3787; 10.3, 8.0 Hz, 1H), 129.51, 121.15, found, 5.17 (dq, J = 9.0, 6.4 Hz, 1H), 116.30, 115.78, 903.3801 5.05 (d, J = 17.1 Hz, 1H), 4.97 (d, J = 10.4 Hz, 109.49, 80.41, 74.75, 1H), 56.08, 51.59, 47.47, 4.71-4.55 (m, 1H), 4.33 (t, J = 8.8 Hz, 33.55, 31.01, 19.70, 1H), 3.95 (s, 3H), 18.34 2.59-2.48 (m, 1H), 2.40 (dt, J = 12.2, 6.8 Hz, 1H), 1.92 (dt, J = 16.2, 8.3 Hz, 1H), 1.86-1.68 (m, 2H), 1.53-1.41 (m, 1H), 1.36 (d, J = 6.4 Hz, 4H) F62 67-69 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.56 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3383, (m/z) 1H), 8.34 (d, J = 5.5 Hz, 172.71, 168.89, 2950, ([M]⁺) 1H), 7.33-7.24 (m, 2H), 162.40, 159.71, 1772, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.43, 146.72, 1744, C₂₉H₃₈N₂O₇, 6.99-6.89 (m, 3H), 5.13-5.01 (m, 141.42, 137.48, 1679, 526.2679; 1H), 4.61 (ddd, J = 10.8, 8.3, 129.57, 120.96, 1509, found, 6.9 Hz, 1H), 4.23-4.15 (m, 115.49, 109.82, 81.64, 1197 526.2687 1H), 3.90 (s, 3H), 74.87, 56.29, 51.66, 2.45-2.32 (m, 1H), 2.40 (s, 3H), 43.19, 36.41, 33.81, 1.91-1.30 (m, 7H), 1.29 (d, J = 6.5 Hz, 28.28, 27.88, 27.64, 3H), 1.28-1.04 (m, 4H), 23.03, 22.06, 20.75, 0.80 (d, J = 6.6 Hz, 3H), 18.92, 18.37 0.79 (d, J = 6.6 Hz, 3H) F63 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.71, 168.87, 2949, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.36, 159.40, 1772, calcd for 1H), 4.95-4.82 (m, 1H), 146.70, 141.44, 1741, C₂₇H₄₀N₂O₇, 4.55 (ddd, J = 10.7, 8.4, 7.0 Hz, 137.44, 109.78, 84.35, 1677, 504.2836; 1H), 3.90 (s, 3H), 78.61, 75.40, 56.27, 1508, found, 3.56-3.32 (m, 2H), 3.09-2.95 (m, 1H), 51.57, 43.56, 36.44, 1368, 504.2842 2.39 (s, 3H), 2.38-2.24 (m, 33.88, 28.07, 27.40, 1196 1H), 1.81-1.43 (m, 6H), 23.02, 22.22, 20.74, 1.41 (d, J = 6.4 Hz, 3H), 18.71, 18.08, 11.12, 1.36-0.92 (m, 6H), 0.89 (d, J = 6.6 Hz, 3.08, 3.00 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.49 (m, 2H), 0.27-0.15 (m, 2H) F64 121-123 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.7 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.75, 168.88, 2936, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.35, 159.40, 1772, calcd for 1H), 4.93-4.78 (m, 1H), 146.70, 141.48, 1742, C₂₆H₄₀N₂O₇, 4.56 (ddd, J = 10.7, 8.4, 7.0 Hz, 137.45, 109.76, 84.57, 1678, 492.2836; 1H), 3.90 (s, 3H), 75.41, 56.27, 51.59, 1507, found, 3.69-3.56 (m, 1H), 3.51-3.39 (m, 1H), 43.50, 36.52, 33.89, 1368, 492.2862 3.07-2.94 (m, 1H), 2.40 (s, 28.10, 27.54, 23.53, 1195 3H), 2.38-2.25 (m, 1H), 23.02, 22.22, 20.74, 1.84-1.25 (m, 9H), 1.41 (d, J = 6.5 Hz, 18.78, 18.09, 10.70 3H), 1.25-0.95 (m, 4H), 0.93 (t, J = 7.4 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F65 60-62 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.9 Hz, ¹³C NMR (CDCl₃) δ 3375, (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.70, 168.87, 2951, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.37, 159.41, 1772, calcd for 1H), 4.92-4.80 (m, 1H), 146.70, 141.42, 1742, C₂₇H₃₉F₃N₂O₇, 4.56 (ddd, J = 10.7, 8.4, 7.0 Hz, 137.46, 127.16 (q, J = 276.2 Hz), 1677, 560.2709; 1H), 3.90 (s, 3H), 109.79, 1508, found, 3.78-3.68 (m, 1H), 3.61-3.49 (m, 1H), 84.83, 75.03, 71.53, 1369, 560.2733 3.08-2.97 (m, 1H), 2.39 (s, 56.27, 51.58, 43.44, 1196 3H), 2.38-2.27 (m, 1H), 36.48, 33.83, 30.81 (q, 2.27-2.11 (m, 2H), 1.88-1.27 (m, J = 29.0 Hz), 28.19, 9H), 1.39 (d, J = 6.4 Hz, 3H), 28.07, 27.52, 23.06 (d, 1.27-0.93 (m, 4H), J = 3.0 Hz), 22.95, 0.93-0.83 (m, 6H) 22.17, 20.74, 18.79, 18.11 ¹⁹F NMR (CDCl₃) δ −66.44 F66 58-60 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.69, 168.87, 2942, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.36, 159.41, 1772, calcd for 1H), 4.92-4.79 (m, 1H), 146.70, 141.44, 1741, C₂₄H₃₆N₂O₇, 4.56 (ddd, J = 10.7, 8.5, 7.1 Hz, 137.45, 109.78, 86.40, 1678, 464.2523; 1H), 3.90 (s, 3H), 3.50 (s, 3H), 75.14, 61.18, 56.27, 1507, found, 2.99-2.87 (m, 1H), 2.40 (s, 51.55, 43.52, 36.48, 1368, 464.2545 3H), 2.38-2.25 (m, 1H), 33.88, 28.24, 28.15, 1196 1.83-1.27 (m, 7H), 1.41 (d, J = 6.4 Hz, 27.29, 23.08, 22.17, 3H), 1.27-0.91 (m, 4H), 20.74, 18.72, 18.03 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F67 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.50 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.57, 168.85, 2939, ([M]⁺) 1H), 7.18-7.07 (m, 2H), 162.38, 161.28 (d, J = 243.6 Hz), 1772, calcd for 7.04-6.90 (m, 3H), 159.40, 1742, C₂₉H₃₅FN₂O₇, 5.00-4.85 (m, 1H), 4.64-4.50 (m, 146.70, 141.38, 1678, 542.2428; 1H), 3.89 (s, 3H), 137.45, 136.31 (d, J = 3.2 Hz), 1508, found, 3.63-3.51 (m, 1H), 3.50-3.37 (m, 1H), 130.14 (d, J = 7.7 Hz), 1314, 542.2436 3.20-3.10 (m, 1H), 115.12 (d J = 21.1 Hz), 1199 3.14-3.04 (m, 1H), 2.39 (s, 3H), 109.80, 2.39-2.20 (m, 2H), 83.72, 78.75, 75.18, 1.90-1.75 (m, 1H), 1.65-1.49 (m, 56.27, 51.47, 46.14, 2H), 1.47-1.33 (m, 1H), 36.04, 33.82, 26.63, 1.45 (d, J = 6.4 Hz, 3H), 20.73, 18.73, 18.06, 1.25-1.05 (m, 2H), 0.96-0.80 (m, 11.16, 3.14, 2.99 1H), 0.65-0.51 (m, 2H), ¹⁹F NMR (CDCl₃) δ −117.47 0.32-0.17 (m, 2H) F68 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.53 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ 3375, (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.59, 168.88, 2939, ([M]⁺) 1H), 7.35-7.27 (m, 2H), 162.41, 161.31 (d, J = 243.6 Hz), 1742, calcd for 7.12-6.89 (m, 8H), 159.55, 1676, C₃₁H₃₃FN₂O₇, 5.17-5.05 (m, 1H), 4.62 (ddd, J = 11.0, 159.44, 146.71, 1508, 564.2272; 8.4, 6.9 Hz, 1H), 141.37, 137.50, 1197 found, 4.36-4.26 (m, 1H), 3.90 (s, 3H), 135.84 (d, J = 3.2 Hz), 564.2280 3.02-2.91 (m, 1H), 2.40 (s, 130.11 (d, J = 7.8 Hz), 3H), 2.39-2.28 (m, 2H), 129.72, 121.26, 2.12-1.99 (m, 1H), 1.74-1.60 (m, 115.47, 115.12 (d, J = 21.1 Hz), 2H), 1.60-1.46 (m, 1H), 109.83, 1.33 (d, J = 6.5 Hz, 3H), 81.01, 74.62, 56.29, 1.30-1.23 (m, 1H), 1.09-0.96 (m, 51.57, 45.70, 36.12, 1H) 33.77, 26.87, 20.75, 18.93, 18.34 ¹⁹F NMR (CDCl₃) δ −117.35 F69 74-76 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.50 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ 3376, (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.47, 168.87, 2940, ([M]⁺) 1H), 7.17-7.06 (m, 2H), 162.41, 161.36 (d, J = 243.8 Hz), 1770, calcd for 7.04-6.91 (m, 3H), 5.86 (tt, J = 55.1, 159.44, 1743, C₂₇H₃₁F₃N₂O₇, 3.9 Hz, 1H), 146.72, 141.32, 1676, 552.2083; 5.00-4.86 (m, 1H), 4.63-4.51 (m, 137.49, 135.85 (d, J = 3.1 Hz), 1508, found, 1H), 4.05-3.90 (m, 1H), 130.14 (d, J = 7.8 Hz), 1199 552.2081 3.89 (s, 3H), 3.85-3.67 (m, 1H), 115.20 (d, J = 21.1 Hz), 3.30-3.20 (m, 1H), 113.88 (t, J = 241.2 Hz), 3.10-2.98 (m, 1H), 2.39 (s, 3H), 109.85, 2.39-2.20 (m, 2H), 85.51, 74.42, 72.59 (t, 1.89-1.76 (m, 1H), 1.68-1.36 (m, J = 27.7 Hz), 56.29, 3H), 1.45 (d, J = 6.4 Hz, 3H), 51.46, 45.79, 35.92, 1.30-1.11 (m, 1H), 33.72, 26.60, 20.74, 0.96-0.81 (m, 1H) 18.82, 18.12 ¹⁹F NMR (CDCl₃) δ −117.20, −125.46 (d, J = 9.5 Hz, 2F) F70 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 527.5 8.63-8.40 (m, 1H), 8.32 (d, J = 5.5 Hz, 172.64, 168.91, ([M + H]⁺) 1H), 7.32-7.25 (m, 2H), 162.38, 159.41, 7.22-7.13 (m, 3H), 6.99 (d, J = 5.5 Hz, 146.70, 141.44, 1H), 4.91 (dq, J = 9.2, 140.86, 137.46, 6.4 Hz, 1H), 4.57 (ddd, J = 10.9, 128.87, 128.34, 8.5, 7.0 Hz, 1H), 125.88, 109.77, 83.70, 3.90 (s, 3H), 3.56 (dd, J = 8.4, 6.3 Hz, 80.65, 75.29, 56.28, 1H), 3.34 (dd, J = 8.4, 6.5 Hz, 51.51, 46.19, 36.73, 1H), 3.21-3.04 (m, 2H), 33.91, 29.28, 26.57, 2.40 (s, 3H), 2.38-2.21 (m, 20.76, 19.56, 19.50, 2H), 1.96-1.78 (m, 2H), 18.80, 18.16 1.61-1.51 (m, 2H), 1.50-1.38 (m, overlapping, 1H), 1.44 (d, J = 6.4 Hz, 3H), 1.29-1.12 (m, 1H), 0.97 (dd, J = 6.7, 5.3 Hz, 6H), 0.92-0.80 (m, 1H) F71 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.56 (d, J = 8.6 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.34 (d, J = 5.5 Hz, 172.71, 168.90, 3379, ([M]⁺) 1H), 7.35-7.22 (m, 2H), 162.40, 159.77, 2943, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.43, 146.72, 2868, C₃₀H₃₈N₂O₇, 6.99-6.89 (m, 3H), 5.07 (dq, J = 9.4, 141.42, 137.48, 1771, 538.2679; 6.5 Hz, 1H), 4.61 (ddd, J = 10.9, 129.58, 120.93, 1737, found, 8.3, 6.9 Hz, 1H), 115.56, 109.82, 1676, 538.2684 4.16 (t, J = 8.7 Hz, 1H), 3.91 (s, 101.26, 101.07, 81.67, 1506, 3H), 2.40 (s, 3H), 74.88, 56.30, 51.67, 1493, 1.92-1.32 (m, 15H), 1.28 (d, J = 6.3 Hz, 42.01, 37.26, 36.85, 1172 3H), 1.20-1.06 (m, 1H), 33.66, 31.77, 27.65, 1.07-0.88 (m, 2H) 25.04, 20.76, 19.07, 18.38 F72 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ — Film) (m/z) 8.53-8.43 (m, 1H), 8.32 (d, J = 5.5 Hz, 3378, ([M]⁺) 1H), 7.15-7.03 (m, 2H), 2938, calcd for 6.99 (d, J = 5.5 Hz, 1H), 1771, C₃₀H₃₈N₂O₈, 6.88-6.72 (m, 2H), 4.91 (dq, J = 9.3, 1742, 554.2628; 6.4 Hz, 1H), 4.56 (dt, J = 10.9, 1678, found, 7.7 Hz, 1H), 3.90 (s, 3H), 1510, 554.2644 3.79 (s, 3H), 3.57 (dd, J = 9.7, 1200 7.0 Hz, 1H), 3.44 (dd, J = 9.7, 6.9 Hz, 1H), 3.15 (t, J = 9.1 Hz, 1H), 3.07 (d, J = 13.1 Hz, 1H), 2.39 (s, 3H), 2.33-2.22 (m, 2H), 1.87-1.76 (m, 1H), 1.55-1.47 (m, 2H), 1.49-1.38 (m, 1H), 1.45 (d, J = 6.5 Hz, 3H), 1.19-1.05 (m, 2H), 0.91-0.80 (m, 1H), 0.64-0.47 (m, 2H), 0.32-0.20 (m, 2H) F73 — — ESIMS ¹H NMR (CDCl₃) δ 8.54 (s, ¹³C NMR (CDCl₃) δ m/z 517 1H), 8.34 (d, J = 5.4 Hz, 1H), 172.71, 168.87, ([M + H]⁺) 7.00 (d, J = 5.5 Hz, 1H), 162.36, 159.40, 4.94-4.82 (m, 1H), 4.55 (dt, J = 10.8, 146.71, 141.44, 7.5 Hz, 1H), 3.90 (s, 3H), 137.44, 109.78, 3.49 (dd, J = 9.7, 7.0 Hz, 1H), 101.25, 101.05, 84.33, 3.36 (dd, J = 9.7, 6.9 Hz, 1H), 78.50, 75.35, 56.28, 2.99 (t, J = 8.9 Hz, 1H), 51.59, 42.29, 37.25, 2.39 (s, 3H), 2.38-2.26 (m, 1H), 36.88, 33.94, 31.83, 1.92-1.66 (m, 4H), 25.09, 25.06, 20.73, 1.64-1.44 (m, 10H), 1.40 (d, J = 6.5 Hz, 18.92, 18.06, 11.13, 3H), 1.35-1.22 (m, 1H), 3.12, 2.93 1.15-0.91 (m, 3H), 0.60-0.50 (m, 2H), 0.21 (dt, J = 6.0, 4.5 Hz, 2H) F74 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (d, J = 6.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.75, 168.89, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.36, 159.41, calcd for 1H), 4.87 (dq, J = 9.3, 6.4 Hz, 146.70, 141.49, C₂₇H₄₀N₂O₇, 1H), 4.55 (ddd, J = 10.8, 8.4, 137.46, 109.75, 84.56, 504.2836; 7.0 Hz, 1H), 3.90 (s, 3H), 75.40, 75.35, 75.33, found, 3.63 (dt, J = 8.7, 6.4 Hz, 1H), 56.28, 51.62, 42.21, 504.2858 3.43 (dt, J = 8.8, 6.8 Hz, 1H), 37.27, 36.83, 33.94, 2.98 (t, J = 8.9 Hz, 1H), 2.40 (s, 31.79, 27.59, 25.10, 3H), 2.33 (dt, J = 13.5, 7.1 Hz, 25.08, 23.54, 20.75, 1H), 1.90-1.42 (m, 17H), 18.96, 18.08, 10.73 1.40 (d, J = 6.4 Hz, 3H), 1.35-1.22 (m, 1H), 1.17-0.97 (m, 1H), 0.93 (t, J = 7.4 Hz, 3H) F75 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.76, 168.89, ([M]⁺) 1H), 7.00 (d, J = 5.4 Hz, 162.36, 159.41, calcd for 1H), 4.87 (dq, J = 9.3, 6.4 Hz, 146.70, 141.49, C₂₈H₄₂N₂O₇, 1H), 4.55 (ddd, J = 10.8, 8.4, 137.45, 109.75, 84.28, 518.2992; 6.9 Hz, 1H), 3.90 (s, 3H), 80.39, 75.46, 56.28, found, 3.46 (dd, J = 8.4, 6.1 Hz, 1H), 51.63, 42.23, 37.23, 518.2998 3.24 (dd, J = 8.4, 6.7 Hz, 1H), 36.73, 33.97, 31.73, 2.96 (t, J = 8.9 Hz, 1H), 2.40 (s, 29.21, 27.58, 25.09, 3H), 2.36-2.26 (m, 1H), 20.75, 19.56, 19.44, 1.92-1.42 (m, 13H), 1.40 (d, J = 6.4 Hz, 18.98, 18.14 3H), 1.36-1.21 (m, 2H), 1.16-0.96 (m, 3H), 0.99-0.83 (m, 6H) F76 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.57 (d, J = 7.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 172.74, 168.92, ([M]⁺) 1H), 7.34-7.23 (m, 2H), 162.39, 159.67, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.42, 146.71, C₂₅H₃₀N₂O₇, 6.95 (dd, J = 7.6, 5.2 Hz, 3H), 141.42, 137.48, 470.2053; 5.09 (dq, J = 9.1, 6.4 Hz, 1H), 129.58, 120.98, found, 4.61 (ddd, J = 10.9, 8.2, 7.0 Hz, 115.48, 109.80, 82.30, 470.2059 1H), 4.15 (t, J = 8.8 Hz, 1H), 74.69, 56.29, 51.70, 3.91 (s, 3H), 2.40 (s, 3H), 37.61, 33.80, 32.47, 2.36 (m, 1H), 1.99-1.86 (m, 1H), 20.76, 19.24, 18.27, 1.68 (ddt, J = 17.7, 14.9, 8.9 Hz, 17.76 3H), 1.38 (m, 1H), 1.30 (d, J = 6.5 Hz, 3H), 1.27 (m, 1H), 1.00 (d, J = 6.9 Hz, 3H) F77 68-70 — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 1H), 172.77, 168.94, [M + H]⁺ 7.42-7.24 (m, 5H), 7.00 (d, J = 5.5 Hz, 162.39, 159.41, calcd for 1H), 4.94 (dq, J = 9.2, 146.72, 141.44, C₂₆H₃₃N₂O₇, 6.4 Hz, 1H), 4.71 (d, J = 10.8 Hz, 138.05, 137.46, 485.2282; 1H), 4.63-4.54 (m, 128.47, 127.82, found, 2H), 3.90 (s, 3H), 3.22 (t, J = 8.9 Hz, 127.74, 109.78, 99.99, 485.2286 1H), 2.40 (s, 3H), 85.30, 75.59, 75.19, 2.39-2.29 (m, 1H), 1.82-1.72 (m, 56.30, 51.63, 37.95, 1H), 1.61 (ddt, J = 19.1, 9.4, 33.89, 32.32, 20.78, 5.7 Hz, 3H), 1.46 (d, J = 6.4 Hz, 19.07, 18.20, 17.79 3H), 1.33 (q, J = 10.8 Hz, 1H), 1.16 (dd, J = 7.3, 3.7 Hz, 1H), 1.07 (d, J = 6.8 Hz, 3H) F78 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.57 (d, J = 7.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 172.65, 168.92, [M + H]⁺ 1H), 7.29 (d, J = 7.6 Hz, 162.39, 159.45, calcd for 2H), 7.01 (d, J = 5.5 Hz, 1H), 146.72, 141.41, C₂₇H₃₅N₂O₈ 6.98-6.90 (m, 3H), 5.07 (dq, 129.62, 121.05, 515.2388, J = 9.1, 6.5 Hz, 1H), 115.38, 109.80, 81.12, found 4.68-4.55 (m, 1H), 4.23 (t, J = 8.8 Hz, 74.82, 70.80, 58.45, 515.2409 1H), 3.91 (s, 3H), 3.37 (t, J = 6.8 Hz, 56.29, 51.63, 40.10, 2H), 3.26 (s, 3H), 33.81, 30.56, 28.18, 2.44-2.34 (m, 4H), 20.76, 19.14, 18.33 1.86 (dddd, J = 23.6, 19.2, 11.4, 6.0 Hz, 3H), 1.77-1.59 (m, 2H), 1.55-1.43 (m, 1H), 1.37 (d, J = 11.6 Hz, 1H), 1.28 (t, J = 6.0 Hz, 3H), 1.23-1.13 (m, 1H) F79  96-100 — ESIMS ¹H NMR (CDCl₃) δ 8.53 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ m/z 561 1H), 8.33 (d, J = 5.5 Hz, 172.55, 168.83, ([M + H]⁺) 1H), 7.35-7.27 (m, 2H), 162.34, 159.62, 7.10-6.94 (m, 8H), 5.12 (dq, 159.36, 146.65, J = 9.1, 6.4 Hz, 1H), 4.63 (dt, J = 10.9, 141.31, 137.42, 7.5 Hz, 1H), 4.33 (t, J = 8.9 Hz, 137.01, 135.34, 1H), 3.89 (s, 3H), 129.62, 128.96, 2.97 (dd, J = 13.3, 3.2 Hz, 128.61, 121.12, 1H), 2.41 (s, 3H), 115.50, 109.76, 81.10, 2.39-2.27 (m, 5H), 2.16-2.02 (m, 1H), 74.64, 56.22, 51.52, 1.72-1.50 (m, 3H), 1.34 (d, J = 6.5 Hz, 45.62, 36.35, 33.75, 3H), 1.33-1.19 (m, 26.67, 20.95, 20.69, 2H) 18.83, 18.31 F80 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (d, J = 7.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.57, 168.89, [M + H]⁺ 1H), 7.39-7.22 (m, 2H), 162.44, 159.44, calcd for 7.10-6.82 (m, 4H), 5.10 (dq, 159.18, 146.77, C₂₆H₃₂O₇BrN₂, J = 9.1, 6.4 Hz, 1H), 141.32, 137.49, 563.1387; 4.61 (ddd, J = 10.9, 8.1, 6.9 Hz, 129.75, 121.34, found, 1H), 4.22 (t, J = 8.7 Hz, 1H), 115.39, 109.91, 80.93, 563.1387 3.89 (s, 3H), 3.45 (ddd, J = 10.0, 74.67, 56.32, 51.66, 7.4, 5.0 Hz, 1H), 41.28, 34.17, 33.58, 3.39-3.26 (m, 1H), 2.40 (s, 3H), 31.56, 28.28, 20.77, 2.43-2.33 (m, 1H), 19.18, 18.27 2.19-1.98 (m, 2H), 1.88-1.75 (m, 2H), 1.75-1.57 (m, 2H), 1.46-1.34 (m, 1H), 1.30 (d, J = 6.5 Hz, 3H), 1.26-1.15 (m, 1H) F81 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 1H), 172.70, 168.92, [M + H]⁺ 7.29 (d, J = 7.9 Hz, 2H), 162.39, 159.67, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.43, 146.71, C₂₆H₃₃O₇N₂, 6.99-6.90 (m, 3H), 5.18-5.00 (m, 141.44, 129.59, 485.2282; 1H), 4.61 (dt, J = 10.6, 7.7 Hz, 120.94, 115.40, found, 1H), 4.20 (t, J = 8.8 Hz, 1H), 109.79, 81.46, 74.84, 485.2288 3.91 (s, 3H), 2.40 (s, 3H), 56.29, 51.65, 44.96, 2.39-2.30 (m, 1H), 1.85 (dt, J = 14.6, 33.86, 27.10, 23.53, 6.9 Hz, 1H), 20.76, 18.82, 18.36, 1.74-1.58 (m, 4H), 1.37 (q, J = 11.5 Hz, 11.89 1H), 1.28 (d, J = 6.4 Hz, 3H), 1.26-1.19 (m, 1H), 1.15 (d, J = 15.0 Hz, 1H), 0.87 (t, J = 7.2 Hz, 3H) F82 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.57 (d, J = 7.4 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 172.57, 168.90, [M + H]⁺ 1H), 7.40-7.27 (m, 2H), 162.43, 159.45, calcd for 7.10-6.86 (m, 4H), 158.92, 146.73, C₂₆H₃₁O₇N₂F₂, 6.06-5.65 (m, 1H), 5.10 (dq, J = 9.1, 141.33, 137.51, 521.2094; 6.5 Hz, 1H), 4.62 (ddd, J = 11.0, 129.84, 121.56, found, 8.3, 6.9 Hz, 1H), 4.22 (t, 116.74 (t, J = 239.3 Hz), 521.2107 J = 8.7 Hz, 1H), 3.91 (s, 3H), 115.26, 109.85, 80.59, 2.48-2.33 (m, 4H), 74.49, 56.30, 51.64, 2.14-1.94 (m, 2H), 1.94-1.71 (m, 37.56, 35.79 (t, J = 20.9 Hz), 3H), 1.71-1.59 (m, 1H), 33.55, 29.50, 1.47-1.34 (m, 1H), 1.30 (d, J = 6.5 Hz, 20.75, 19.30, 18.24 3H), 1.29-1.22 (m, 1H) F83 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 1H), 172.67, 168.92, [M + H]⁺ 7.00 (d, J = 5.4 Hz, 1H), 162.36, 159.40, calcd for 4.99-4.79 (m, 1H), 4.56 (dt, J = 10.7, 146.70, 141.43, C₂₈H₄₁O₈N₂, 7.7 Hz, 1H), 3.91 (s, 3H), 137.45, 109.76, 83.99, 533.2857; 3.55-3.38 (m, 4H), 3.25 (dq, 78.39, 75.47, 75.33, found, J = 6.6, 3.3 Hz, 2H), 3.06 (t, J = 8.8 Hz, 69.12, 56.28, 51.55, 533.2857 1H), 2.40 (s, 3H), 40.50, 33.86, 30.65, 2.33 (dt, J = 13.3, 6.3 Hz, 1H), 28.19, 20.76, 18.96, 1.99 (d, J = 9.7 Hz, 1H), 18.06, 11.09, 10.66, 1.78-1.60 (m, 3H), 1.57-1.45 (m, 3.18, 3.02, 2.95, 2.88 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.30 (q, J = 11.8, 11.4 Hz, 1H), 1.06 (ddd, J = 12.9, 11.1, 6.7 Hz, 3H), 0.60-0.48 (m, 4H), 0.29-0.15 (m, 4H) F84 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 7.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.20-7.97 (m, 172.64, 168.87, [M + H]⁺ 1H), 7.06 (t, J = 7.9 Hz, 2H), 162.39, 159.42, calcd for 6.78 (d, J = 5.4 Hz, 1H), 158.86, 146.73, C₃₀H₃₈O₈N₂, 6.76-6.64 (m, 3H), 4.71 (dq, J = 8.9, 141.40, 137.46, 555.2701; 6.4 Hz, 1H), 4.36 (dt, J = 10.7, 129.42, 120.60, found, 7.2 Hz, 1H), 3.80 (td, J = 7.1, 114.49, 109.82, 83.94, 555.2713 6.3, 2.7 Hz, 2H), 3.68 (s, 78.22, 75.25, 66.18, 3H), 3.27 (dd, J = 9.6, 7.2 Hz, 56.29, 51.56, 40.29, 1H), 3.21 (dd, J = 9.6, 6.8 Hz, 34.67, 33.81, 30.35, 1H), 2.91 (t, J = 8.9 Hz, 1H) 28.23, 20.75, 19.07, 2.18 (s, 3H), 2.13 (dt, J = 13.2, 18.08, 11.09, 3.16, 6.8 Hz, 1H), 2.06-1.90 (m, 2.93 1H), 1.71-1.55 (m, 2H), 1.48 (dddd, J = 25.6, 20.4, 14.3, 7.2 Hz, 2H), 1.34 (dt, J = 22.3, 9.7 Hz, 1H), 1.22 (d, J = 6.4 Hz, 3H), 1.18-1.02 (m, 1H), 0.86 (ddt, J = 12.2, 7.3, 4.1 Hz, 2H), 0.39-0.29 (m, 2H), −0.01 (q, J = 4.8 Hz, 2H) F85 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (d, J = 6.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (dd, J = 5.4, 173.54, 168.83, [M + H]⁺ 1.5 Hz, 1H), 7.00 (d, J = 5.5 Hz, 162.26, 159.39, calcd for 1H), 5.10-4.92 (m, 146.70, 141.43, C₂₀H₂₇O₇N₂, 1H), 4.67-4.38 (m, 1H), 137.42, 109.81, 86.83, 407.1813; 3.89 (d, J = 1.5 Hz, 3H), 73.26, 67.69, 56.27, found, 3.85-3.75 (m, 1H), 3.75-3.62 (m, 53.00, 39.69, 36.09, 407.1829 1H), 3.42 (dd, J = 9.5, 6.3 Hz, 35.75, 32.56, 21.77, 1H), 2.40 (d, J = 1.2 Hz, 3H), 20.73, 18.35 2.39-2.29 (m, 1H), 2.13-1.93 (m, 2H), 1.89 (dd, J = 17.2, 7.8 Hz, 1H), 1.74 (td, J = 14.9, 14.0, 5.0 Hz, 1H), 1.63 (t, J = 13.5 Hz, 1H), 1.57-1.44 (m, 1H), 1.41 (d, J = 6.3 Hz, 3H), 1.36 (dd, J = 12.8, 6.0 Hz, 1H), 1.26 (s, 1H) F86 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.59 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.35 (d, J = 5.4 Hz, 1H), 172.71, 168.92, [M + H]⁺ 7.27 (d, J = 2.9 Hz, 2H), 162.40, 159.43, calcd for 7.01 (d, J = 5.5 Hz, 1H), 6.93 (dd, J = 13.2, 159.32, 146.72, C₂₆H₃₁N₂O₇, 7.6 Hz, 3H), 5.77 (ddd, 141.38, 138.52, 483.2126; J = 18.2, 10.3, 8.1 Hz, 1H), 129.49, 121.09, found, 5.16 (dt, J = 9.1, 6.4 Hz, 1H), 116.17, 115.78, 483.2144 5.04 (d, J = 17.1 Hz, 1H), 109.81, 80.51, 74.46, 4.95 (d, J = 10.3 Hz, 1H), 56.29, 51.68, 47.45, 4.69-4.57 (m, 1H), 4.30 (t, J = 8.8 Hz, 33.80, 31.19, 20.76, 1H), 3.91 (s, 3H), 19.75, 18.30 2.58-2.46 (m, 1H), 2.40 (s, 3H), 2.40-2.33 (m, 1H), 1.89 (dq, J = 14.3, 7.4 Hz, 1H), 1.77 (td, J = 16.3, 15.5, 8.5 Hz, 2H), 1.46-1.24 (m, 5H) F87 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.49 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (dd, J = 5.4, 172.64, 168.90, [M + H]⁺ 0.6 Hz, 1H), 162.38, 159.41, calcd for 7.33-7.26 (m, 2H), 7.22-7.13 (m, 3H), 146.70, 141.43, C₂₇H₃₅N₂O₇, 6.99 (d, J = 5.5 Hz, 1H), 140.75, 137.46, 499.2439; 4.90 (dq, J = 9.2, 6.4 Hz, 1H), 128.87, 128.34, found, 4.57 (ddd, J = 10.9, 8.4, 7.0 Hz, 125.90, 109.78, 84.20, 499.2449 1H), 3.89 (d, J = 0.9 Hz, 3H), 75.21, 69.22, 56.28, 3.82 (dq, J = 8.8, 6.9 Hz, 1H), 51.51, 45.94, 36.91, 3.63 (dq, J = 8.9, 7.0 Hz, 1H), 33.90, 26.64, 20.76, 3.17 (t, J = 9.1 Hz, 1H), 18.75, 18.02, 15.73 3.09 (dd, J = 13.2, 3.4 Hz, 1H), 2.39 (s, 3H), 2.35 (dd, J = 13.4, 11.8 Hz, 1H), 2.32-2.20 (m, 1H), 1.83 (ddq, J = 12.2, 7.7, 3.7 Hz, 1H), 1.70-1.52 (m, 2H), 1.50-1.38 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.25 (t, J = 7.0 Hz, 3H), 1.21-1.12 (m, 1H), 0.87 (ddt, J = 18.0, 6.4, 3.2 Hz, 1H) F88 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.49 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.63, 168.90, [M + H]⁺ 1H), 7.31-7.26 (m, 1H), 162.38, 159.41, calcd for 7.22-7.14 (m, 3H), 6.99 (d, J = 5.4 Hz, 146.70, 141.43, C₂₈H₃₇N₂O₇, 1H), 4.90 (dq, J = 9.2, 140.81, 137.46, 513.2595; 6.4 Hz, 1H), 4.57 (ddd, J = 10.9, 128.87, 128.34, found, 8.4, 7.0 Hz, 1H), 125.88, 109.77, 83.99, 513.2606 3.89 (s, 3H), 3.73 (dt, J = 8.7, 6.5 Hz, 75.59, 75.25, 56.28, 1H), 3.59-3.41 (m, 1H), 51.51, 46.06, 36.82, 3.16 (t, J = 9.1 Hz, 1H), 33.90, 26.61, 23.60, 3.10 (dd, J = 13.3, 3.3 Hz, 1H), 20.76, 18.77, 18.09, 2.39 (s, 3H), 2.35 (dd, J = 13.3, 10.75 11.8 Hz, 1H), 2.31-2.20 (m, 1H), 1.84 (ddt, J = 12.1, 8.2, 3.9 Hz, 1H), 1.72-1.51 (m, 5H), 1.49-1.40 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.21-1.11 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.91-0.79 (m, 1H) F89 48-50 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3375, (m/z) 1H), 8.29 (d, J = 5.4 Hz, 172.82, 170.26, 2951, ([M]⁺) 1H), 7.34-7.22 (m, 2H), 162.97, 160.25, 1746, calcd for 7.01-6.88 (m, 4H), 5.75 (s, 159.71, 145.76, 1675, C₃₀H₄₀N₂O₈, 2H), 5.14-5.02 (m, 1H), 143.94, 142.42, 1492, 556.2785; 4.62 (ddd, J = 10.8, 8.1, 7.0 Hz, 129.57, 120.96, 1202 found, 1H), 4.26-4.17 (m, 1H), 115.49, 109.63, 89.49, 556.2794 3.91 (s, 3H), 2.46-2.33 (m, 1H), 81.63, 74.87, 56.19, 2.07 (s, 3H), 1.93-1.31 (m, 51.93, 43.23, 36.40, 7H), 1.30 (d, J = 6.4 Hz, 3H), 33.62, 28.27, 27.88, 1.28-1.04 (m, 4H), 0.80 (d, J = 6.6 Hz, 27.57, 23.04, 22.06, 3H), 0.79 (d, J = 6.6 Hz, 20.88, 18.94, 18.39 3H) F90 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.86, 170.24, 2953, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.92, 160.22, 1745, calcd for 1H), 5.74 (s, 2H), 145.74, 143.88, 1678, C₂₈H₄₄N₂O₈, 4.94-4.80 (m, 1H), 4.57 (ddd, J = 10.7, 142.48, 109.57, 89.49, 1506, 536.3098; 8.1, 7.0 Hz, 1H), 3.91 (s, 3H), 84.30, 80.42, 75.43, 1203 found, 3.46 (dd, J = 8.4, 6.3 Hz, 1H), 56.17, 51.86, 43.53, 536.3107 3.27 (dd, J = 8.4, 6.5 Hz, 1H), 36.54, 33.67, 29.17, 3.07-2.95 (m, 1H), 28.09, 28.02, 27.55, 2.41-2.28 (m, 1H), 2.07 (s, 3H), 22.96, 22.27, 20.85, 1.91-1.39 (m, 7H), 1.41 (d, J = 6.4 Hz, 19.50, 19.45, 18.84, 3H), 1.38-0.95 (m, 18.16 5H), 0.95-0.81 (m, 12H) F91 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.84, 170.27, 2949, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.95, 160.23, 1742, calcd for 1H), 5.74 (s, 2H), 145.76, 143.90, 1676, C₂₈H₄₂N₂O₈, 4.96-4.81 (m, 1H), 4.63-4.50 (m, 1H), 142.50, 109.57, 89.52, 1504, 534.2941; 3.91 (s, 3H), 3.57-3.31 (m 84.36, 78.65, 75.41, 1368, found, 2H), 3.09-2.97 (m, 1H), 56.18, 51.85, 43.61, 1201 534.2945 2.43-2.25 (m, 1H), 2.07 (s, 3H), 36.44, 33.71, 28.08, 1.85-1.45 (m, 6H), 1.42 (d, J = 6.4 Hz, 27.34, 23.03, 22.22, 3H), 1.38-0.92 (m, 20.88, 18.74, 18.11, 6H), 0.89 (d, J = 6.6 Hz, 3H), 11.13, 3.09, 3.02 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.51 (m, 2H), 0.27-0.17 (m, 2H) F92 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.87, 170.27, 2937, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.93, 160.24, 1744, calcd for 1H), 5.74 (s, 2H), 145.74, 143.92, 1678, C₂₇H₄₂N₂O₈, 4.93-4.81 (m, 1H), 4.57 (ddd, J = 10.8, 142.51, 109.56, 89.54, 1504, 522.2941; 8.1, 7.0 Hz, 1H), 3.91 (s, 3H), 84.58, 75.42, 56.17, 1369, found, 3.69-3.58 (m, 1H), 51.86, 43.54, 36.51, 1202 522.2965 3.52-3.41 (m, 1H), 3.08-2.98 (m, 33.71, 28.10, 27.48, 1H), 2.41-2.28 (m, 1H), 23.54, 23.03, 22.22, 2.07 (s, 3H), 1.83-1.26 (m, 9H), 20.88, 18.81, 18.11, 1.42 (d, J = 6.5 Hz, 3H), 10.71 1.26-0.95 (m, 4H), 0.94 (t, J = 7.4 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F93 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3384, (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.82, 170.26, 2951, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.95, 160.24, 1747, calcd for 1H), 5.74 (s, 2H), 145.74, 143.92, 1678, C₂₈H₄₁F₃N₂O₈, 4.93-4.80 (m, 1H), 4.57 (ddd, J = 10.8, 142.45, 127.16 (q, J = 276.1 Hz), 1506, 590.2815; 8.1, 7.0 Hz, 1H), 3.91 (s, 3H), 109.59, 1371, found, 3.79-3.68 (m, 1H), 89.51, 84.84, 75.03, 1252 590.2828 3.61-3.50 (m, 1H), 3.09-2.98 (m, 71.54, 56.17, 51.85, 1H), 2.41-2.28 (m, 1H), 43.47, 36.47, 33.63, 2.28-2.12 (m, 2H), 2.07 (s, 3H), 30.81 (q, J = 28.9 Hz), 1.91-1.29 (m, 9H), 1.40 (d, J = 6.4 Hz, 28.19, 28.07, 27.46, 3H), 1.29-0.92 (m, 23.05 (q, J = 3.2 Hz), 4H), 0.92-0.83 (m, 6H) 22.95, 22.16, 20.86, 18.83, 18.13 ¹⁹F NMR (CDCl₃) δ −66.44 F94 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 173.03, 170.28, 2952, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.92, 160.25, 1743, calcd for 1H), 5.74 (s, 2H), 145.75, 143.93, 1678, C₂₉H₄₄N₂O₈, 4.90-4.78 (m, 1H), 4.57 (ddd, J = 10.9, 142.54, 109.55, 89.57, 1505, 548.3098; 8.0, 6.6 Hz, 1H), 83.55, 82.90, 75.85, 1369, found, 4.08-3.99 (m, 1H), 3.91 (s, 3H), 3.14 (dd, 56.18, 52.12, 42.89, 1202 548.3112 J = 9.1, 7.9 Hz, 1H), 36.86, 33.60, 32.75, 2.42-2.28 (m, 1H), 2.07 (s, 3H), 32.50, 28.27, 23.04, 1.86-0.98 (m, 19H), 1.43 (d, 22.97, 22.96, 22.37, J = 6.5 Hz, 3H), 0.89 (d, J = 6.6 Hz, 20.89, 19.19, 18.36 3H), 0.88 (d, J = 6.6 Hz, 3H) F95 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.82, 170.26, 2942, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.94, 160.24, 1744, calcd for 1H), 5.74 (s, 2H), 145.75, 143.92, 1678, C₂₅H₃₈N₂O₈, 4.92-4.78 (m, 1H), 4.58 (ddd, J = 10.7, 142.50, 109.57, 89.53, 1504, 494.2628; 8.1, 7.1 Hz, 1H), 3.91 (s, 3H), 86.42, 75.14, 61.21, 1369, found, 3.50 (s, 3H), 3.00-2.89 (m, 56.18, 51.82, 43.57, 1202 494.2648 1H), 2.42-2.28 (m, 1H), 36.48, 33.70, 28.25, 2.07 (s, 3H), 1.83-1.27 (m, 7H), 28.16, 27.25, 23.09, 1.43 (d, J = 6.4 Hz, 3H), 22.18, 20.88, 18.75, 1.27-0.91 (m, 4H), 0.90 (d, J = 6.6 Hz, 18.06 3H), 0.88 (d, J = 6.6 Hz, 3H) F96 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.32 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 176.16, 172.86, 2953, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 170.27, 162.92, 1735, calcd for 1H), 5.74 (s, 2H), 160.26, 145.70, 1679, C₃₀H₄₄N₂O₉, 5.09-4.94 (m, 1H), 4.93-4.82 (m, 1H), 144.01, 142.39, 1505, 576.3047; 4.68-4.54 (m, 1H), 3.91 (s, 109.60, 89.53, 76.13, 1368, found, 3H), 2.82-2.67 (m, 1H), 73.39, 56.18, 51.83, 1202 576.3060 2.45-2.31 (m, 1H), 2.07 (s, 3H), 44.09, 41.93, 36.34, 1.99-1.39 (m, 13H), 33.51, 30.06, 29.98, 1.39-1.14 (m, 4H), 1.26 (d, J = 6.3 Hz, 27.99, 27.90, 27.45, 3H), 1.14-0.96 (m, 2H), 25.70, 25.68, 22.89, 0.92-0.77 (m, 6H) 22.19, 20.87, 18.74, 17.55 F97 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.84, 170.27, 2921, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.94, 160.24, 1743, calcd for 1H), 5.74 (s, 2H), 145.76, 143.92, 1677, C₃₀H₄₄N₂O₈, 4.96-4.81 (m, 1H), 4.57 (ddd, J = 10.8, 142.53, 109.56, 89.54, 1504, 560.3098; 8.1, 7.0 Hz, 1H), 3.91 (s, 3H), 84.40, 78.52, 75.41, 1314, found, 3.49 (dd, J = 9.6, 7.0 Hz, 1H), 56.18, 51.84, 40.15, 1202 560.3097 3.37 (dd, J = 9.6, 6.8 Hz, 1H), 38.32, 35.07, 34.60, 3.06-2.94 (m, 1H), 33.77, 32.35, 27.46, 2.43-2.27 (m, 1H), 2.07 (s, 3H), 26.70, 26.50, 26.17, 1.80-1.42 (m, 11H), 1.41 (d, 20.89, 18.81, 18.10, J = 6.4 Hz, 3H), 11.15, 3.17, 2.94 1.37-0.69 (m, 9H), 0.63-0.49 (m, 2H), 0.28-0.16 (m, 2H) F98 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.69, 170.23, 2939, ([M]⁺) 1H), 7.18-7.08 (m, 2H), 162.95, 161.27 (d, J = 243.6 Hz), 1746, calcd for 7.02-6.91 (m, 3H), 5.73 (s, 160.22, 1678, C₃₀H₃₇FN₂O₈, 2H), 4.99-4.85 (m, 1H), 145.75, 143.88, 1508, 572.2534; 4.58 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.41, 136.32 (d, J = 3.2 Hz), 1314, found, 1H), 3.90 (s, 3H), 3.58 (dd, J = 9.7, 130.14 (d, J = 7.8 Hz), 1203 572.2546 7.0 Hz, 1H), 3.45 (dd, J = 9.7, 115.11 (d, J = 21.0 Hz), 6.8 Hz, 1H), 109.61, 3.21-3.14 (m, 1H), 3.14-3.05 (m, 1H), 89.46, 83.72, 78.77, 2.40-2.25 (m, 2H), 2.06 (s, 75.18, 56.17, 51.75, 3H), 1.89-1.76 (m, 1H), 46.16, 36.04, 33.62, 1.64-1.50 (m, 2H), 1.47-1.36 (m, 26.60, 20.85, 18.76, 1H), 1.46 (d, J = 6.5 Hz, 3H), 18.08, 11.16, 3.14, 1.31-1.06 (m, 2H), 3.00 0.96-0.81 (m, 1H), 0.64-0.52 (m, 2H), 0.32-0.19 (m, 2H) F99 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.70, 170.24, 2940, ([M]⁺) 1H), 7.36-7.26 (m, 2H), 162.97, 161.29 (d, J = 243.7 Hz), 1751, calcd for 7.11-6.89 (m, 8H), 5.74 (s, 160.25, 1678, C₃₂H₃₅FN₂O₈, 2H), 5.18-5.06 (m, 1H), 159.55, 145.75, 1508, 594.2377; 4.64 (ddd, J = 11.0, 8.0, 6.9 Hz 143.95, 142.35, 1204 found, 1H), 4.39-4.28 (m, 1H), 135.85 (d, J = 3.2 Hz), 594.2395 3.90 (s, 3H), 3.02-2.91 (m, 1H), 130.10 (d, J = 7.8 Hz), 2.43-2.29 (m, 2H), 129.71, 121.25, 2.14-1.99 (m, 1H), 2.07 (s, 3H), 115.46, 115.10 (d, J = 21.1 Hz), 1.74-1.62 (m, 2H), 109.65, 1.62-1.46 (m, 1H), 1.34 (d, J = 6.4 Hz, 89.46, 80.98, 74.59, 3H), 1.31-1.23 (m, 1H), 56.18, 51.84, 45.73, 1.10-0.98 (m, 1H) 36.10, 33.55, 26.79, 20.85, 18.94, 18.34 F100 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.5 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.71, 170.26, 2938, ([M]⁺) 1H), 7.17-7.07 (m, 2H), 162.96, 161.30 (d, J = 243.6 Hz), 1745, calcd for 7.02-6.90 (m, 3H), 160.24, 1677, C₂₉H₃₅FN₂O₈, 6.03-5.88 (m, 1H), 5.74 (s, 2H), 145.75, 143.93, 1507, 558.2377; 5.33 (dq, J = 17.2, 1.6 Hz, 142.43, 136.27 (d, J = 3.3 Hz), 1202 found, 1H), 5.21 (dq, J = 10.4, 1.3 Hz, 134.31, 558.2390 1H), 4.99-4.86 (m, 1H), 130.14 (d, J = 7.7 Hz), 4.59 (ddd, J = 10.9, 8.1, 7.0 Hz, 117.14, 115.12 (d, J = 21.1 Hz), 1H), 4.29 (ddt, J = 12.2, 109.60, 5.6, 1.4 Hz, 1H), 4.11 (ddt, J = 12.1, 89.50, 84.16, 75.04, 5.5, 1.4 Hz, 1H), 3.90 (s, 74.70, 56.18, 51.77, 3H), 3.29-3.18 (m, 1H), 45.99, 36.11, 33.63, 3.12-3.01 (m, 1H), 2.40-2.24 (m, 26.61, 20.88, 18.82, 2H), 2.07 (s, 3H), 18.15 1.89-1.74 (m, 1H), 1.65-1.50 (m, 2H), ¹⁹F NMR (CDCl₃) δ −117.47 1.47 (d, J = 6.5 Hz, 3H), 1.47-1.34 (m, 1H), 1.28-1.14 (m, 1H), 0.97-0.78 (m, 1H) F101 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3381, (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.72, 170.24, 2937, ([M]⁺) 1H), 7.17-7.07 (m, 2H), 162.95, 161.27 (d, J = 243.5 Hz), 1745, calcd for 7.02-6.90 (m, 3H), 5.74 (s, 160.23, 1677, C₂₉H₃₇FN₂O₈, 2H), 4.98-4.84 (m, 1H), 145.75, 143.90, 1508, 560.2534; 4.58 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.43, 136.40 (d, J = 3.1 Hz), 1372, found, 1H), 3.90 (s, 3H), 3.73 (dt, J = 8.6, 130.13 (d, J = 7.7 Hz), 1203 560.2541 6.5 Hz, 1H), 3.52 (dt, J = 8.7, 115.09 (d, J = 21.1 Hz), 6.7 Hz, 1H), 109.60, 3.21-3.11 (m, 1H), 3.11-3.01 (m, 1H), 89.49, 83.92, 75.62, 2.41-2.25 (m, 2H), 2.06 (s, 75.19, 56.18, 51.77, 3H), 1.86-1.72 (m, 1H), 46.17, 36.00, 33.64, 1.70-1.51 (m, 4H), 1.46 (d, J = 6.4 Hz, 26.61, 23.58, 20.86, 3H), 1.46-1.35 (m, 1H), 18.81, 18.09, 10.73 1.30-1.13 (m, 1H), 0.98 (t, J = 7.4 Hz, ¹⁹F NMR (CDCl₃) δ −117.52 3H), 0.94-0.79 (m, 1H) F102 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.73, 170.27, 2957, ([M]⁺) 1H), 7.18-7.05 (m, 2H), 162.95, 161.28 (d, J = 243.5 Hz), 1744, calcd for 7.02-6.90 (m, 3H), 5.74 (s, 160.24, 1677, C₃₀H₃₉FN₂O₈, 2H), 4.98-4.83 (m, 1H), 145.75, 143.93, 1508, 574.2690; 4.58 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.44, 136.44 (d, J = 3.2 Hz), 1369, found, 1H), 3.90 (s, 3H), 3.56 (dd, J = 8.4, 130.13 (d, J = 7.8 Hz), 1203 574.2691 6.3 Hz, 1H), 3.33 (dd, J = 8.4, 115.11 (d, J = 21.0 Hz), 6.5 Hz, 1H), 109.58, 3.19-3.10 (m, 1H), 3.10-3.01 (m, 1H), 89.52, 83.65, 80.70, 2.41-2.24 (m, 2H), 2.07 (s, 75.24, 56.18, 51.77, 3H), 1.97-1.71 (m, 2H), 46.31, 35.91, 33.66, 1.63-1.51 (m 2H), 1.45 (d, J = 6.4 Hz, 29.27, 26.56, 20.88, 3H), 1.45-1.34 (m, 1H), 19.53, 19.49, 18.84, 1.29-1.14 (m, 1H), 0.97 (d, J = 6.8 Hz, 18.16 3H), 0.96 (d, J = 6.8 Hz, ¹⁹F NMR (CDCl₃) δ −117.53 3H), 0.93-0.79 (m, 1H) F103 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.59, 170.25, 2940, ([M]⁺) 1H), 7.18-7.05 (m, 2H), 162.98, 161.35 (d, J = 243.8 Hz), 1749, calcd for 7.03-6.89 (m, 3H), 5.94 (tt, J = 55.2, 160.25, 1677, C₂₈H₃₃F₃N₂O₈, 3.9 Hz, 1H), 5.73 (s, 145.76, 143.94, 1508, 582.2189; 2H), 5.02-4.84 (m, 1H), 142.34, 135.86 (d, J = 3.2 Hz), 1203 found, 4.58 (ddd, J = 10.9, 8.1, 6.9 Hz, 130.14 (d, J = 7.8 Hz), 582.2191 1H), 4.06-3.91 (m, 1H), 115.19 (d, J = 21.1 Hz), 3.90 (s, 3H), 3.86-3.72 (m, 1H), 113.88 (t, J = 241.2 Hz), 3.32-3.21 (m, 1H), 109.65, 3.11-2.98 (m, 1H), 2.44-2.24 (m, 89.47, 85.53, 74.41, 2H), 2.06 (s, 3H), 72.60 (t, J = 27.6 Hz), 1.92-1.76 (m, 1H), 1.68-1.38 (m, 3H), 56.19, 51.74, 45.81, 1.47 (d, J = 6.4 Hz, 3H), 35.93, 33.51, 26.57, 1.30-1.15 (m, 1H), 0.98-0.80 (m, 20.86, 18.86, 18.14 1H) ¹⁹F NMR (CDCl₃) δ −117.21 F104 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 7.8 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 176.11, 172.73, 2943, ([M]⁺) 1H), 7.12-7.02 (m, 2H), 170.27, 162.94, 1732, calcd for 7.02-6.90 (m, 3H), 5.73 (s, 161.35 (d, J = 244.0 Hz), 1677, C₃₂H₃₉FN₂O₉, 2H), 5.11-4.94 (m, 2H), 160.26, 145.71, 1507, 614.2640; found, 4.62 (ddd, J = 11.0, 8.0, 7.0 Hz, 144.01, 142.33, 1201 614.2649 1H), 3.90 (s, 3H), 135.59 (d, J = 3.2 Hz), 2.80-2.69 (m, 1H), 2.69-2.61 (m, 1H), 130.07 (d, J = 7.8 Hz), 2.42-2.29 (m, 2H), 2.07 (s, 115.22 (d, J = 21.2 Hz), 3H), 2.01-1.43 (m, 11H), 109.63, 89.51, 75.54, 1.36-1.16 (m, 2H), 1.29 (d, J = 5.6 Hz, 73.16, 56.18, 51.75, 3H), 1.05-0.91 (m, 44.16, 44.01, 35.93, 1H) 33.44, 30.06, 30.04, 26.82, 25.72, 25.70, 20.86, 18.73, 17.55 ¹⁹F NMR (CDCl₃) δ −117.11 F105 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 176.42, 172.70, 2940, ([M]⁺) 1H), 7.12-7.02 (m, 2H), 170.23, 162.94, 1734, calcd for 7.02-6.90 (m, 3H), 5.73 (s, 161.34 (d, J = 244.1 Hz), 1677, C₃₀H₃₇FN₂O₉, 2H), 5.10-4.97 (m, 2H), 160.25, 145.70, 1508, 588.2483; found, 4.62 (ddd, J = 10.9, 8.0, 7.0 Hz, 143.98, 142.30, 1201 588.2484 1H), 3.91 (s, 3H), 2.65 (dd, J = 14.0, 135.54 (d, J = 3.2 Hz), 3.6 Hz, 1H), 2.58 (hept, J = 7.0 Hz), 130.05 (d, J = 7.7 Hz), 1H), 2.43-2.29 (m, 115.20 (d, J = 21.2 Hz), 2H), 2.07 (s, 3H), 109.64, 89.46, 75.47, 2.00-1.85 (m, 1H), 1.77-1.44 (m, 3H), 73.07, 56.17, 51.73, 1.35-1.17 (m, 1H), 1.29 (d, J = 5.8 Hz, 44.13, 35.84, 34.19, 3H), 1.22 (d, J = 7.1 Hz, 33.40, 26.73, 20.84, 3H), 1.22 (d, J = 6.9 Hz, 19.06, 18.97, 18.70, 3H); 1.06-0.91 (m, 1H) 17.48 ¹⁹F NMR (CDCl₃) δ −117.09 F106 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ m/z 557.3 1H), 8.26 (d, J = 5.4 Hz, 172.76, 170.27, ([M + H]⁺) 1H), 7.32-7.25 (m, 2H), 162.95, 160.23, 7.23-7.13 (m, 3H), 6.94 (d, J = 5.4 Hz, 145.75, 143.90, 1H), 5.74 (s, 2H), 142.47, 140.86, 4.91 (dq, J = 9.3, 6.5 Hz, 1H), 128.87, 128.34, 4.58 (ddd, J = 10.9, 8.2, 7.0 Hz, 125.88, 109.58, 89.52, 1H), 3.90 (s, 3H), 83.71, 80.66, 75.29. 3.57 (dd, J = 8.4, 6.2 Hz, 1H), 56.18, 51.79, 46.21, 3.34 (dd, J = 8.4, 6.5 Hz, 1H), 36.74, 33.71, 29.28, 3.16 (t, J = 9.1 Hz, 1H), 3.11 (dd, J = 13.3, 26.55, 20.88, 19.56, 3.2 Hz, 1H), 19.50, 18.84, 18.18 2.41-2.26 (m, 2H), 2.06 (s, 3H), 1.97-1.77 (m, 2H), 1.58 (tt, J = 8.6, 2.6 Hz, 2H), 1.46 (d, J = 6.4 Hz, 3H), 1.49-1.39 (m, 1H, overlapping), 1.27-1.13 (m, 1H), 0.97 (dd, J = 6.7, 5.4 Hz, 6H), 0.91-0.83 (m, 1H) F107 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 555.4 8.36-8.20 (m, 2H), 7.33-7.23 (m, 172.73, 170.27, ([M + H]⁺) 2H), 7.23-7.12 (m, 3H), 162.95, 160.23, 6.94 (d, J = 5.4 Hz, 1H), 5.73 (s, 145.75, 143.89, 2H), 4.93 (dq, J = 9.1, 6.4 Hz, 142.45, 140.73, 1H), 4.58 (ddd, J = 10.9, 8.1, 128.89, 128.35, 7.0 Hz, 1H), 3.90 (s, 3H), 125.90, 109.58, 89.50, 3.59 (dd, J = 9.7, 7.0 Hz, 1H), 83.80, 78.76, 75.24, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 56.18, 51.77, 46.07, 3.28-3.04 (m, 2H), 2.42-2.23 (m, 36.89, 33.70, 26.58, 2H), 2.06 (s, 3H), 1.89 (ddt, J = 12.2, 20.88, 18.76, 18.11, 8.3, 3.9 Hz, 1H), 11.18, 3.16, 3.01 1.66-1.50 (m, 2H), 1.49-1.38 (m, overlapping, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.23-1.06 (m, 2H), 0.94-0.80 (m, 1H), 0.65-0.53 (m, 2H), 0.34-0.17 (m, 2H) F108 — — ESIMS ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.0 Hz, ¹³C NMR (75 MHz, m/z 577.5 1H), 8.27 (d, J = 5.4 Hz, CDCl₃) δ 172.83, ([M + H]⁺) 1H), 7.35-7.21 (m, 3H), 170.35, 163.08, 7.21-7.08 (m, 3H), 160.35, 159.76, 7.06-6.91 (m, 4H), 5.74 (s, 2H), 145.85, 144.04, 5.12 (dq, J = 9.1, 6.5 Hz, 1H), 142.52, 140.36, 4.63 (ddd, J = 10.9, 8.1, 7.0 Hz, 129.81, 128.92, 1H), 4.36 (t, J = 8.9 Hz, 128.43, 126.07, 1H), 3.90 (s, 3H), 3.02 (dd, J = 13.4, 121.32, 115.65, 3.3 Hz, 1H), 109.75, 89.59, 81.26, 2.46-2.29 (m, 2H), 2.16-2.08 (m, 1H), 74.78, 56.28, 51.97, 2.06 (s, 3H), 1.76-1.63 (m, 45.79, 37.01, 33.72, 2H), 1.63-1.49 (m, 1H), 26.86, 20.97, 19.06, 1.35 (d, J = 6.5 Hz, 3H), 18.49 1.31-1.21 (m, 2H), 1.09-0.96 (m, 1H) F109 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 8.34-8.24 (m, 2H), 7.34-7.24 (m, 172.78, 170.30, [M + H]⁺ 2H), 7.24-7.13 (m, 3H), 162.97, 160.25, calcd for 6.94 (d, J = 5.4 Hz, 1H), 5.73 (s, 145.77, 143.91, C₂₉H₃₉N₂O₈, 2H), 4.91 (dq, J = 9.2, 6.4 Hz, 142.49, 140.82, 543.2701; 1H), 4.58 (ddd, J = 10.9, 8.1, 128.89, 128.35, found, 7.0 Hz, 1H), 3.90 (s, 3H), 125.89, 109.59, 89.51, 543.2707 3.78-3.70 (m, 1H), 3.57-3.48 (m, 84.00, 75.61, 75.26, 1H), 3.22-3.14 (m, 1H), 56.18, 51.78, 46.08, 3.11 (dd, J = 13.2, 3.3 Hz, 1H), 36.82, 33.70, 26.58, 2.41-2.24 (m, 2H), 2.06 (s, 23.60, 20.88, 18.80, 3H), 1.90-1.79 (m, 1H), 18.11, 10.75. 1.73-1.53 (m, 4H), 1.50-1.38 (m, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.27-1.15 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.94-0.81 (m, 1H) F110 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 569.3 1H), 8.26 (d, J = 5.4 Hz, 172.95, 170.26, ([M + H]⁺) 1H), 7.35-7.23 (m, 2H), 162.92, 160.23, 7.23-7.12 (m, 3H), 6.93 (d, J = 5.4 Hz, 145.75, 143.91, 1H), 4.89 (dq, J = 9.1, 142.48, 141.13, 6.5 Hz, 1H), 4.56 (ddd, J = 11.1, 128.89, 128.34, 8.1, 6.7 Hz, 1H), 125.82, 109.57, 89.53, 4.13 (ddd, J = 9.5, 4.7, 2.7 Hz, 1H), 83.85, 82.36, 75.69, 3.90 (s, 3H), 3.40-3.24 (m, 56.17, 52.01, 45.31, 1H), 3.20 (dd, J = 13.3, 3.3 Hz, 36.92, 33.53, 32.84, 1H), 2.36-2.19 (m, 2H), 32.56, 29.70, 27.84, 2.06 (s, 3H), 1.89-1.67 (m, 23.03, 22.98, 20.87, 7H), 1.64-1.53 (m, 4H), 19.13, 18.37 1.48 (d, J = 6.5 Hz, 3H), 1.45-1.36 (m, 1H), 1.23-1.06 (m, 2H), 1.00-0.83 (m, 2H) F111 — — ESIMS ¹H NMR (CDCl₃) δ 8.27 (t, J = 7.0 Hz, ¹³C NMR (CDCl₃) δ m/z 529.3 2H), 7.24 (dt, J = 39.0, 172.76, 170.27, ([M + H]⁺) 7.6 Hz, 5H), 6.94 (d, J = 5.4 Hz, 162.95, 160.24, 1H), 5.73 (s, 2H), 145.76, 143.91, 4.91 (dq, J = 12.9, 6.8 Hz, 1H), 142.47, 140.76, 4.58 (dt, J = 10.7, 7.6 Hz, 1H), 128.88, 128.34, 3.90 (s, 3H), 3.82 (t, J = 7.8 Hz, 125.90, 109.58, 89.52, 1H), 3.70-3.56 (m, 1H), 84.22, 75.21, 69.24, 3.19 (t, J = 9.0 Hz, 1H), 56.18, 51.78, 45.97, 3.10 (dd, J = 13.1, 3.6 Hz, 1H), 36.92, 33.71, 26.61, 2.53-2.23 (m, 2H), 2.06 (s, 20.88, 18.78, 18.04, 3H), 1.84 (qd, J = 8.0, 3.7 Hz, 15.74 1H), 1.58 (dt, J = 9.6, 5.1 Hz, 2H), 1.47 (t, J = 5.8 Hz, 4H), 1.25 (t, J = 6.3 Hz, 4H), 1.01-0.78 (m, 1H) F112 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 559.2 8.31-8.24 (m, 2H), 7.31-7.25 (m, 172.70, 170.26, ([M + H]⁺) 2H), 7.23-7.14 (m, 3H), 162.94, 160.23, 6.93 (d, J = 5.4 Hz, 1H), 5.73 (s, 145.75, 143.92, 2H), 4.94 (dq, J = 9.2, 6.4 Hz, 142.46, 140.78, 1H), 4.58 (ddd, J = 10.9, 8.1, 128.91, 128.33, 7.0 Hz, 1H), 3.95 (ddd, J = 9.9, 125.88, 109.57, 89.52, 6.0, 3.7 Hz, 1H), 3.90 (s, 84.75, 75.06, 72.83, 3H), 3.72 (ddd, J = 10.4, 5.6, 72.16, 59.09, 56.18, 3.4 Hz, 1H), 3.62-3.51 (m, 51.76, 45.85, 36.78, 2H), 3.40 (s, 3H), 3.23 (t, J = 9.1 Hz, 33.70, 26.55, 20.88, 1H), 3.19-3.09 (m, 18.81, 18.17 1H), 2.42-2.24 (m, 2H), 2.06 (s, 3H), 1.96-1.85 (m, 1H), 1.63-1.53 (m, 2H), 1.48 (d, J = 6.4 Hz, 3H), 1.46-1.39 (m, 1H), 1.25-1.15 (m, 1H), 0.93-0.81 (m, 1H) F113 — — ESIMS ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 563.6 1H), 8.28 (d, J = 5.4 Hz, 172.86, 170.26, ([M + H]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.94, 160.24, 1H), 5.74 (s, 2H), 4.87 (dq, J = 9.2, 145.74, 143.91, 6.4 Hz, 1H), 4.57 (ddd, J = 10.8, 142.55, 109.56, 89.54, 8.2, 7.1 Hz, 1H), 84.33, 80.37, 75.48, 3.91 (s, 3H), 3.46 (dd, J = 8.4, 6.1 Hz, 56.17, 51.87, 40.04, 1H), 3.24 (dd, J = 8.4, 6.7 Hz, 38.15, 35.08, 34.60, 1H), 2.98 (t, J = 8.8 Hz, 33.75, 32.27, 29.21, 1H), 2.42-2.27 (m, 1H), 27.47, 26.69, 26.52, 2.07 (s, 3H), 1.83 (dt, J = 13.2, 6.6 Hz, 26.20, 20.87, 19.58, 1H), 1.77-1.55 (m, 8H), 19.47, 18.87, 18.16 1.41 (d, J = 6.3 Hz, 3H), 1.37-1.11 (m, 8H), 1.01-0.87 (m, 8H), 0.77 (t, J = 11.2 Hz, 1H) F114 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.75, 170.30, ([M]⁺) 1H), 7.36-7.23 (m, 2H), 162.96, 160.25, calcd for 7.08-6.99 (m, 4H), 159.67, 157.83, C₃₃H₃₈N₂O₉, 6.99-6.91 (m, 2H), 6.80 (d, J = 8.6 Hz, 145.74, 143.97, 606.2577; 2H), 5.74 (s, 2H), 142.39, 132.22, found, 5.12 (dq, J = 9.2, 6.4 Hz, 1H), 129.69, 121.18, 606.2585 4.63 (ddd, J = 10.9, 8.0, 6.8 Hz, 115.55, 113.73, 1H), 4.33 (t, J = 8.9 Hz, 1H), 109.60, 89.52, 81.13, 3.91 (s, 3H), 3.77 (s, 3H), 74.71, 56.19, 55.20, 3.00-2.90 (m, 1H), 2.42-2.25 (m, 51.85, 45.83, 35.96, 2H), 2.07 (s, 3H), 33.65, 26.67, 20.89, 1.73-1.63 (m, 2H), 1.63-1.50 (m, 2H), 18.91, 18.39 1.34 (d, J = 6.4 Hz, 3H), 1.33-1.17 (m, 1H), 1.06-0.97 (m, 1H) F115 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz, 172.84, 170.28, ([M]⁺) 1H), 7.35-7.25 (m, 2H), 162.97, 160.26, calcd for 6.99-6.90 (m, 4H), 5.75 (s, 159.78, 145.75, C₃₁H₄₀N₂O₈, 2H), 5.07 (dq, J = 9.2, 6.5 Hz, 143.97, 142.46, 568.2785; 1H), 4.62 (ddd, J = 10.9, 8.0, 129.58, 120.93, found, 6.9 Hz, 1H), 4.25-4.12 (m, 115.56, 109.61, 89.54, 568.2786 1H), 3.91 (s, 3H), 2.41 (dtd, J = 13.7, 81.67, 74.89, 56.19, 7.0, 1.4 Hz, 1H), 51.94, 42.05, 37.27, 2.07 (s, 3H), 1.92-1.76 (m, 3H), 36.85, 33.71, 33.66, 1.76-1.59 (m, 4H), 31.77, 27.59, 25.04, 1.60-1.32 (m, 7H), 1.30 (d, J = 6.5 Hz, 20.88, 19.10, 18.39. 3H), 1.20-1.06 (m, 1H), 1.08-0.90 (m, 2H) F116 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 8.42-8.15 (m, 2H), 7.09 (d, J = 8.6 Hz, 172.74, 170.28, ([M]⁺) 2H), 6.94 (d, J = 5.4 Hz, 162.94, 160.23, calcd for 1H), 6.83 (d, J = 8.6 Hz, 2H), 157.82, 145.75, C₃₁H₄₀N₂O₉, 5.73 (s, 2H), 4.92 (dq, J = 9.1, 143.91, 142.46, 584.2734; 6.4 Hz, 1H), 4.58 (ddd, J = 10.9, 132.68, 129.74, found, 8.1, 7.0 Hz, 1H), 3.90 (s, 113.77, 109.57, 89.52, 584.2744 3H), 3.79 (s, 3H), 3.58 (dd, J = 9.7, 83.80, 78.77, 75.25, 7.0 Hz, 1H), 3.45 (dd, J = 9.7, 56.18, 55.23, 51.76, 6.8 Hz, 1H), 3.17 (t, J = 9.0 Hz, 46.21, 35.92, 33.72, 1H), 3.08 (dd, J = 13.4, 26.52, 20.88, 18.75, 3.4 Hz, 1H), 18.10, 11.18, 3.16, 2.41-2.22 (m, 2H), 2.06 (s, 3H), 3.00 1.91-1.76 (m, 1H), 1.61-1.52 (m, 2H), 1.52-1.40 (m, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.23-1.17 (m, 1H), 1.17-1.07 (m, 1H), 0.91-0.77 (m, 1H), 0.64-0.54 (m, 2H), 0.29-0.21 (m, 2H) F117 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.85, 170.28, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.94, 160.24, calcd for 1H), 5.74 (s, 2H), 4.89 (dq, J = 9.3, 145.75, 143.93, C₂₉H₄₂N₂O₈, 6.4 Hz, 1H), 4.57 (dt, J = 10.8, 142.52, 109.55, 89.56, 546.2941; 7.3 Hz, 1H), 3.91 (s, 3H), 84.35, 78.54, 75.38, found, 3.50 (dd, J = 9.6, 7.0 Hz, 1H), 56.18, 51.87, 42.35, 546.2956 3.36 (dd, J = 9.6, 6.8 Hz, 1H), 37.26, 36.89, 33.96, 3.01 (t, J = 8.9 Hz, 1H), 33.77, 31.84, 27.51, 2.46-2.26 (m, 1H), 2.07 (s, 3H), 25.10, 25.07, 20.89, 1.91-1.43 (m, 13H), 1.42 (d, 18.96, 18.10, 11.14, J = 6.5 Hz, 3H), 3.14, 2.94 1.36-1.26 (m, 1H), 1.18-0.92 (m, 4H), 0.60-0.49 (m, 2H), 0.21 (dt, J = 6.0, 4.5 Hz, 2H) F118 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.28 (dd, J = 9.8, ¹³C NMR (CDCl₃) δ (m/z) 6.7 Hz, 2H), 7.08 (d, J = 8.5 Hz, 172.78, 170.28, ([M]⁺) 2H), 6.94 (d, J = 5.4 Hz, 162.96, 160.25, calcd for 1H), 6.88-6.71 (m, 2H), 157.82, 145.75, C₃₁H₄₂N₂O₉, 5.74 (s, 2H), 4.96-4.73 (m, 143.92, 142.49, 586.2890; 1H), 4.58 (ddd, J = 10.9, 8.1, 132.83, 129.73, found, 7.0 Hz, 1H), 3.90 (s, 3H), 113.77, 109.59, 89.53, 586.2905 3.79 (s, 3H), 3.56 (dd, J = 8.4, 6.2 Hz, 83.73, 80.65, 75.31, 1H), 3.34 (dd, J = 8.4, 6.5 Hz, 56.18, 55.23, 51.81, 1H), 3.14 (t, J = 9.0 Hz, 46.35, 35.79, 33.73, 1H), 3.07-2.99 (m, 1H), 31.60, 29.28, 26.53, 2.41-2.20 (m, 2H), 2.06 (s, 3H), 22.67, 20.88, 19.56, 1.95-1.84 (m, 1H), 19.50, 18.85, 18.18, 1.84-1.65 (m, 2H), 1.66-1.52 (m, 14.13 2H), 1.45 (d, J = 6.4 Hz, 3H), 1.32-1.21 (m, 1H), 1.00-0.93 (m, 6H), 0.88-0.82 (m, 1H) F119 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.28 (dd, J = 8.8, ¹³C NMR (CDCl₃) δ (m/z) 6.6 Hz, 2H), 7.08 (d, J = 8.5 Hz, 172.76, 170.27, ([M]⁺) 2H), 6.94 (d, J = 5.4 Hz, 162.94, 160.23, calcd for 1H), 6.83 (d, J = 8.6 Hz, 157.80, 145.74, C₃₀H₄₀N₂O₉, 2H), 5.74 (s, 2H), 4.90 (dq, J = 9.2, 143.91, 142.47, 572.2734; 6.4 Hz, 1H), 4.58 (ddd, J = 10.9, 132.77, 129.72, found, 8.1, 7.0 Hz, 1H), 113.75, 109.57, 89.52, 572.2720 3.90 (s, 3H), 3.79 (s, 3H), 3.73 (dt, 84.00, 75.60, 75.26, J = 8.7, 6.5 Hz, 1H), 3.52 (dt, J = 8.7, 56.18, 55.23, 51.78, 6.7 Hz, 1H), 3.16 (t, J = 9.0 Hz, 46.21, 35.86, 33.73, 1H), 3.04 (dd, J = 13.4, 26.54, 23.60, 20.88, 3.3 Hz, 1H), 18.79, 18.11, 10.75 2.43-2.22 (m, 2H), 2.06 (s, 3H), 1.79 (ddq, J = 12.2, 7.4, 3.7 Hz, 1H), 1.70-1.52 (m, 5H), 1.45 (d, J = 6.4 Hz, 3H), 1.25-1.13 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.93-0.81 (m, 1H) F120 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.78, 170.29, 3379, ([M]⁺) 1H), 7.30 (dd, J = 1.9, 0.9 Hz, 162.93, 160.24, 2954, calcd for 1H), 6.94 (d, J = 5.4 Hz, 154.69, 145.75, 1744, C₂₈H₃₈N₂O₉, 1H), 6.28 (dd, J = 3.1, 1.9 Hz, 143.93, 142.45, 1677, 546.2577; 1H), 6.02 (d, J = 3.1 Hz, 1H), 141.01, 110.09, 1505, found, 5.74 (s, 2H), 4.92 (dq, J = 9.2, 109.56, 106.04, 89.54, 1202 546.2602 6.4 Hz, 1H), 4.58 (ddd, J = 10.8, 83.46, 80.26, 75.19, 8.0, 6.8 Hz, 1H), 3.90 (s, 56.18, 51.80, 43.22, 3H), 3.50 (dd, J = 8.4, 6.5 Hz, 33.63, 29.34, 29.20, 1H), 3.30 (dd, J = 8.4, 6.4 Hz, 27.89, 20.89, 19.49, 1H), 3.14 (t, J = 9.0 Hz, 1H), 19.46, 18.85, 18.17 3.01 (dd, J = 14.7, 3.5 Hz, 1H), 2.52 (dd, J = 14.6, 11.2 Hz, 1H), 2.31 (dt, J = 12.6, 6.4 Hz, 1H), 2.07 (s, 3H), 2.01-1.91 (m, 1H), 1.87 (dt, J = 13.2, 6.6 Hz, 1H), 1.55 (dddd, J = 20.1, 12.2, 10.0, 5.2 Hz, 3H), 1.44 (d, J = 6.4 Hz, 3H), 1.36-1.20 (m, 1H), 1.06-0.95 (m, 1H), 0.94 (d, J = 6.7 Hz, 6H) F121 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 176.47, 172.86, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 170.29, 162.93, calcd for 1H), 5.74 (d, J = 0.8 Hz, 2H), 160.27, 145.71, C₂₉H₄₂N₂O₉, 5.00 (dq, J = 9.4, 6.3 Hz, 1H), 144.03, 142.42, 562.2890; 4.85 (t, J = 9.1 Hz, 1H), 109.59, 89.56, 76.08, found, 4.61 (ddd, J = 10.9, 7.9, 6.9 Hz, 73.32, 56.18, 51.84, 562.2888 1H), 3.91 (s, 3H), 2.57 (hept, J = 7.0 Hz, 40.64, 37.00, 36.53, 1H), 2.39 (dtd, J = 13.2, 34.29, 33.68, 33.57, 6.5, 1.9 Hz, 1H), 2.07 (s, 31.86, 27.31, 25.03, 3H), 1.91-1.27 (m, 13H), 25.02, 20.87, 19.11, 1.25 (d, J = 6.3 Hz, 3H), 18.95, 18.86, 17.50 1.19 (dd, J = 7.0, 1.6 Hz, 6H), 1.13-1.00 (m, 3H), 1.00-0.86 (m, 1H) F122 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.85, 170.24, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.93, 160.23, calcd for 1H), 5.74 (s, 2H), 4.87 (dq, J = 9.2, 145.74, 143.89, C₂₈H₄₂N₂O₈, 6.4 Hz, 1H), 4.57 (ddd, J = 10.8, 142.50, 109.58, 89.50, 534.2941; 8.1, 6.9 Hz, 1H), 84.55, 75.37, 75.32, found, 3.91 (s, 3H), 3.64 (dt, J = 8.7, 6.4 Hz, 56.17, 51.87, 42.22, 534.2945 1H), 3.44 (dt, J = 8.7, 6.7 Hz, 37.25, 36.81, 33.92, 1H), 3.00 (t, J = 8.8 Hz, 33.72, 31.77, 27.54, 1H), 2.41-2.29 (m, 1H), 25.08, 25.06, 23.53, 2.07 (s, 3H), 1.94-1.39 (m, 15H), 20.86, 18.98, 18.08, 1.41 (d, J = 6.3 Hz, 3H), 10.72 1.37-1.22 (m, 1H), 1.17-0.98 (m, 3H), 0.94 (t, J = 7.4 Hz, 3H) F123 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.86, 170.25, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.93, 160.23, calcd for 1H), 5.74 (s, 2H), 4.87 (dq, J = 9.2, 145.74, 143.90, C₂₉H₄₄N₂O₈, 6.4 Hz, 1H), 4.57 (ddd, J = 10.8, 142.52, 109.57, 89.53, 548.3098; 8.1, 6.9 Hz, 1H), 84.28, 80.39, 75.44, found, 3.91 (s, 3H), 3.47 (dd, J = 8.4, 6.1 Hz, 56.17, 51.89, 42.25, 548.3094 1H), 3.24 (dd, J = 8.4, 6.7 Hz, 37.22, 36.72, 33.96, 1H), 2.98 (t, J = 8.8 Hz, 33.74, 31.72, 29.20, 1H), 2.41-2.29 (m, 1H), 27.54, 25.09, 25.07, 2.07 (s, 3H), 1.90-1.38 (m, 11H), 20.87, 19.55, 19.44, 1.41 (d, J = 6.5 Hz, 3H), 19.01, 18.15 1.37-1.21 (m, 2H), 1.17-0.96 (m, 5H), 0.92 (t, J = 6.8 Hz, 6H) F124 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.85, 170.29, ([M]⁺) 1H), 7.34-7.24 (m, 2H), 162.96, 160.26, calcd for 7.01-6.88 (m, 4H), 5.75 (s, 159.68, 145.75, C₂₆H₃₂N₂O₈, 2H), 5.09 (dq, J = 9.1, 6.4 Hz, 143.97, 142.41, 500.2159; 1H), 4.63 (dt, J = 10.9, 7.1 Hz, 129.59, 120.98, found, 1H), 4.17 (t, J = 8.8 Hz, 1H), 115.48, 109.60, 89.54, 500.2162 3.91 (s, 3H), 2.41 (dt, J = 13.0, 82.29, 74.69, 56.19, 6.6 Hz, 1H), 2.07 (s, 3H), 51.95, 37.67, 33.62, 1.93 (dd, J = 9.2, 5.4 Hz, 1H), 32.38, 20.89, 19.26, 1.80-1.61 (m, 3H), 1.40 (dt, J = 13.5, 18.30, 17.76 10.7 Hz, 1H), 1.31 (d, J = 6.4 Hz, 3H), 1.29-1.24 (m, 1H), 1.01 (d, J = 6.9 Hz, 3H) F125 142-147 — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.89, 170.32, [M + H]⁺ 1H), 7.40-7.28 (m, 5H), 162.96, 160.25, calcd for 6.95 (d, J = 5.4 Hz, 1H), 145.77, 143.94, C₂₇H₃₅N₂O₈, 5.75 (s, 2H), 4.95 (dq, J = 9.2, 6.4 Hz, 142.47, 138.05, 515.2388; 1H), 4.72 (d, J = 10.8 Hz, 128.47, 127.82, found, 1H), 4.64-4.55 (m, 2H), 127.75, 109.58, 89.56, 515.2390 3.91 (s, 3H), 3.23 (t, J = 8.9 Hz, 85.30, 75.60, 75.20, 1H), 2.37 (dt, J = 13.3, 6.7 Hz, 56.19, 51.89, 37.99, 1H), 2.07 (s, 3H), 33.71, 32.27, 20.90, 1.82-1.72 (m, 1H), 1.70-1.58 (m, 3H), 19.10, 18.22, 17.79 1.48 (d, J = 6.4 Hz, 3H), 1.41-1.30 (m, 1H), 1.18 (dt, J = 7.5, 3.5 Hz, 1H), 1.08 (d, J = 6.8 Hz, 3H) F126 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 571 8.25-8.16 (m, 2H), 7.06-6.94 (m, 171.71, 169.22, ([M + H]⁺) 4H), 6.86 (d, J = 5.4 Hz, 1H), 161.90, 159.19, 5.66 (s, 2H), 4.83 (dq, J = 9.3, 144.70, 142.86, 6.4 Hz, 1H), 4.50 (dt, J = 11.0, 141.42, 136.64, 7.5 Hz, 1H), 3.82 (s, 3H), 134.27, 127.98, 3.49 (dd, J = 8.4, 6.2 Hz, 1H), 127.68, 108.54, 88.47, 3.26 (dd, J = 8.4, 6.5 Hz, 1H), 82.67, 79.59, 74.25, 3.07 (t, J = 9.0 Hz, 1H), 2.99 (dd, J = 13.2, 55.13, 50.74, 45.17, 3.1 Hz, 1H), 2.24 (s, 35.19, 32.67, 28.22, 5H), 1.99 (s, 3H), 25.46, 19.97, 19.83, 1.90-1.69 (m, 2H), 1.59-1.45 (m, 2H), 18.51, 18.45, 17.77, 1.44-1.30 (m, 4H), 17.13 1.17-1.05 (m, 1H), 0.92-0.86 (m, 6H), 0.83-0.73 (m, 1H) F127 55-60 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 569 1H), 8.26 (d, J = 5.4 Hz, 172.65, 170.17, ([M + H]⁺) 1H), 7.12-7.04 (m, 4H), 162.86, 160.14, 6.94 (d, J = 5.4 Hz, 1H), 145.67, 143.80, 5.73 (s, 1H), 4.92 (dq, J = 9.2, 6.4 Hz, 142.35, 137.47, 1H), 4.58 (ddd, J = 10.9, 135.25, 128.95, 8.2, 7.0 Hz, 1H), 3.90 (s, 3H), 128.66, 109.51, 89.40, 3.59 (dd, J = 9.7, 7.0 Hz, 1H), 83.70, 78.66, 75.16, 3.45 (dd, J = 9.7, 6.9 Hz, 1H), 56.10, 51.68, 46.01, 3.17 (t, J = 9.1 Hz, 1H), 36.30, 33.61, 26.44, 3.10 (dd, J = 13.3, 3.3 Hz, 1H), 20.93, 20.79, 18.65, 2.40-2.23 (m, 5H), 2.06 (s, 18.02, 11.09, 3.07, 3H), 1.94-1.79 (m, 1H), 2.92 1.65-1.39 (m, 5H), 1.33-1.08 (m, 3H), 0.92-0.82 (m, 2H), 0.65-0.54 (m, 2H), 0.25 (dtd, J = 5.5, 3.9, 3.5, 1.6 Hz, 2H) F128 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 170.35, 167.84, ([M + Na]⁺) 1H), 6.95 (d, J = 5.4 Hz, 160.52, 157.81, calcd for 1H), 5.74 (s, 2H), 4.90 (dq, J = 9.1, 143.31, 141.51, C₂₅H₃₇FN₂O₈Na, 6.4 Hz, 1H), 4.58 (ddt, J = 9.4, 140.02, 107.14, 87.11, 535.2426; 5.9, 4.6 Hz, 2H), 81.42, 81.36, 79.73, found, 4.50-4.39 (m, 1H), 3.91 (s, 3H), 77.78, 72.81, 53.74, 535.2423 3.45 (dd, J = 8.4, 6.6 Hz, 1H), 49.43, 37.34, 37.30, 3.26 (dd, J = 8.4, 6.4 Hz, 1H), 31.13, 29.17, 28.98, 3.14-3.02 (m, 1H), 2.36 (dt, J = 12.9, 26.73, 26.26, 18.44, 6.7 Hz, 1H), 2.07 (s, 17.02, 16.98, 16.74, 3H), 2.06-1.98 (m, 1H), 15.69 1.84 (dp, J = 13.4, 6.7 Hz, 1H), 1.78-1.60 (m, 4H), 1.57 (s, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.39-1.29 (m, 1H), 1.10 (dd, J = 14.3, 5.7 Hz, 1H), 0.92 (d, J = 6.8 Hz, 6H) F129 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz, 171.99, 169.51, ([M + H]⁺) 1H), 7.33-7.27 (m, 2H), 162.20, 159.49, calcd for 7.25-7.21 (m, 2H), 158.57, 158.01, C₃₃H₃₉N₂O₉, 7.02-6.87 (m, 5H), 6.86-6.77 (m, 144.98, 143.21, 607.2650; 2H), 5.75 (s, 2H), 141.63, 128.91, found, 5.19-5.04 (m, 1H), 4.64 (dt, J = 10.9, 7.0 Hz, 128.61, 120.40, 607.2664 1H), 4.29 (t, J = 8.7 Hz, 119.82, 114.64, 1H), 3.96 (t, J = 6.0 Hz, 2H), 113.68, 108.83, 88.76, 3.91 (s, 3H), 2.41 (dt, J = 12.6, 80.39, 74.00, 65.27, 6.4 Hz, 1H), 2.07 (s, 5H), 55.41, 51.14, 39.45, 1.98-1.84 (m, 1H), 1.84-1.64 (m, 32.81, 29.76, 27.68, 3H), 1.40 (q, J = 11.3 Hz, 1H), 20.11, 18.54, 17.56 1.32 (d, J = 6.5 Hz, 3H), 1.29-1.20 (m, 1H) F130 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz, 172.77, 170.29, ([M + H]⁺) 1H), 7.33-7.27 (m, 2H), 162.97, 160.26, calcd for 6.98-6.91 (m, 4H), 5.75 (s, 159.47, 145.75, C₂₈H₃₇N₂O₉, 2H), 5.08 (dq, J = 9.1, 6.5 Hz, 143.99, 142.43, 545.2494; 1H), 4.63 (dt, J = 10.9, 7.0 Hz, 129.62, 121.06, found, 1H), 4.25 (t, J = 8.8 Hz, 1H), 115.39, 109.61, 89.54, 545.2519 3.91 (s, 3H), 3.38 (t, J = 6.8 Hz, 81.12, 74.83, 70.80, 2H), 3.26 (s, 3H), 2.41 (dt, 58.44, 56.19, 51.90, J = 12.4, 6.3 Hz, 1H), 2.07 (s, 40.15, 33.63, 30.56, 3H), 1.99-1.78 (m, 3H), 28.14, 20.89, 19.18, 1.78-1.61 (m, 2H), 1.49 (ddt, J = 13.6, 18.35 10.1, 6.6 Hz, 1H), 1.44-1.33 (m, 1H), 1.30 (d, J = 6.5 Hz, 3H), 1.23-1.14 (m, 1H) F131 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.79, 170.28, [M + H]⁺ 1H), 6.94 (d, J = 5.4 Hz, 162.95, 160.25, calcd for 1H), 5.74 (s, 2H), 145.75, 143.95, C₂₆H₄₁N₂O₈S, 4.96-4.83 (m, 1H), 4.58 (dt, J = 10.8, 7.0 Hz, 142.48, 109.57, 89.55, 541.2578; 1H), 3.91 (s, 3H), 83.95, 80.40, 75.34, found, 3.45 (dd, J = 8.4, 6.5 Hz, 1H), 56.18, 51.86, 42.31, 541.2581 3.27 (dd, J = 8.4, 6.5 Hz, 1H), 33.59, 32.17, 29.99, 3.04 (t, J = 8.7 Hz, 1H), 2.59 (ddd, 29.20, 27.81, 20.89, J = 12.8, 9.7, 4.6 Hz, 1H), 19.49, 18.99, 18.14, 2.49-2.41 (m, 1H), 2.41-2.31 (m, 15.39 1H), 2.10 (s, 3H), 2.07 (s, 3H), 1.94 (ddd, J = 11.9, 9.5, 6.9 Hz, 1H), 1.84 (dt, J = 13.2, 6.6 Hz, 1H), 1.80-1.60 (m, 3H), 1.52 (ddt, J = 13.9, 9.7, 4.7 Hz, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.34 (q, J = 11.1 Hz, 1H), 1.09-1.00 (m, 1H), 0.92 (dd, J = 6.7, 1.0 Hz, 6H) F132 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.82, 170.27, [M + Na]⁺ 1H), 6.95 (d, J = 5.4 Hz, 162.94, 160.25, calcd for 1H), 5.74 (s, 2H), 4.88 (dq, J = 9.1, 145.74, 143.94, C₂₆H₄₀O₉N₂Na, 6.4 Hz, 1H), 4.58 (dt, J = 10.8, 142.50, 109.57, 89.55, 547.2626; 7.3 Hz, 1H), 3.91 (s, 3H), 84.05, 80.35, 75.38, found, 3.42 (q, J = 7.6, 6.9 Hz, 3H), 71.28, 58.49, 56.18, 547.2652 3.32 (s, 3H), 3.32-3.26 (m, 51.88, 40.27, 33.65, 1H), 3.05 (t, J = 8.8 Hz, 1H), 30.41, 29.17, 28.37, 2.36 (dt, J = 13.2, 6.5 Hz, 1H), 20.88, 19.51, 19.43, 2.07 (s, 3H), 2.02-1.91 (m, 19.11, 18.15 1H), 1.84 (dq, J = 13.2, 6.6 Hz, 1H), 1.67 (tq, J = 20.9, 8.5, 6.2 Hz, 3H), 1.59-1.44 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.33 (q, J = 11.2 Hz, 1H), 1.10-0.99 (m, 1H), 0.92 (dd, J = 6.7, 2.6 Hz, 6H) F133 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.88, 170.27, [M + H]⁺ 1H), 6.95 (d, J = 5.4 Hz, 162.94, 160.24, calcd for 1H), 5.74 (s, 2H), 4.88 (dq, J = 9.2, 145.75, 143.93, C₂₅H₃₉O₈N₂, 6.4 Hz, 1H), 142.53, 109.56, 89.56, 495.2701; 4.68-4.49 (m, 1H), 3.91 (s, 3H), 3.43 (dd, 84.25, 80.41, 75.44, found, J = 8.4, 6.6 Hz, 1H), 3.27 (dd, 56.17, 51.88, 45.22, 495.2717 J = 8.4, 6.4 Hz, 1H), 3.01 (t, J = 8.9 Hz, 33.74, 29.18, 27.13, 1H), 2.35 (dt, J = 12.8, 23.27, 20.88, 19.49, 6.9 Hz, 1H), 2.07 (s, 3H), 19.45, 18.81, 18.18, 1.83 (dd, J = 13.2, 6.6 Hz, 11.96 1H), 1.80-1.69 (m, 2H), 1.65-1.47 (m, 2H), 1.41 (d, J = 6.4 Hz, 4H), 1.38-1.27 (m, 1H), 1.22 (ddd, J = 13.2, 10.8, 7.3 Hz, 1H), 1.05-0.95 (m, 1H), 0.91 (d, J = 6.8 Hz, 9H) F134 71-75 — ESIMS ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 591 1H), 8.27 (d, J = 5.4 Hz, 172.65, 170.18, ([M + H]⁺) 1H), 7.34-7.28 (m, 2H), 162.89, 160.16, 7.09-6.95 (m, 7H), 6.94 (d, J = 5.4 Hz, 159.61, 145.67, 1H), 5.74 (s, 2H), 143.86, 142.30, 5.12 (dq, J = 9.2, 6.4 Hz, 1H), 137.00, 135.31, 4.63 (ddd, J = 11.0, 8.1, 7.0 Hz, 129.60, 128.94, 1H), 4.34 (t, J = 8.9 Hz, 128.60, 121.10, 1H), 3.89 (s, 3H), 2.97 (dd, J = 13.4, 115.48, 109.55, 89.40, 3.2 Hz, 1H), 81.08, 74.61, 56.10, 2.43-2.27 (m, 5H), 2.15-2.02 (m, 4H), 51.77, 45.65, 36.33, 1.77-1.48 (m, 2H), 1.35 (d, J = 6.5 Hz, 33.54, 26.58, 20.93, 3H), 1.32-1.19 (m, 20.79, 18.31, 14.05 2H) F135 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.69, 170.27, [M + H]⁺ 1H), 7.30 (dd, J = 8.6, 7.4 Hz, 162.99, 160.26, calcd for 2H), 7.07-6.87 (m, 4H), 159.18, 145.79, C₂₇H₃₄O₈BrN₂, 5.74 (s, 2H), 5.11 (dq, J = 9.1, 143.95, 142.33, 593.1493; 6.5 Hz, 1H), 4.63 (dt, J = 10.9, 129.75, 121.33, found, 6.9 Hz, 1H), 4.24 (t, J = 8.7 Hz, 115.38, 109.69, 89.48, 593.1499 1H), 3.91 (s, 3H), 80.92, 74.65, 56.22, 3.46 (ddd, J = 10.0, 7.3, 5.0 Hz, 51.92, 41.32, 34.14, 1H), 3.41-3.28 (m, 1H), 33.39, 31.57, 28.20, 2.50-2.36 (m, 1H), 2.20-1.99 (m, 20.89, 19.20, 18.28 5H), 1.93-1.75 (m, 2H), 1.70 (dt, J = 16.7, 7.1 Hz, 2H), 1.51-1.36 (m, 1H), 1.31 (d, J = 6.5 Hz, 3H), 1.27-1.15 (m, 1H) F136 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz, 172.82, 170.29, [M + H]⁺ 1H), 7.30 (d, J = 7.7 Hz, 162.97, 160.26, calcd for 2H), 6.94 (dd, J = 7.2, 4.7 Hz, 159.68, 145.75, C₂₇H₃₅O₈N₂, 4H), 5.75 (s, 2H), 143.98, 142.44, 515.2388; 5.21-5.02 (m, 1H), 4.63 (dt, J = 10.8, 7.5 Hz, 129.59, 120.95, found, 1H), 4.22 (t, J = 8.8 Hz, 115.41, 109.60, 89.55, 515.2393 1H), 3.91 (s, 3H), 2.41 (dt, J = 12.7, 81.44, 74.84, 56.19, 7.1 Hz, 1H), 2.07 (s, 3H), 51.91, 45.00, 33.68, 1.95-1.82 (m, 1H), 1.64 (dd, 27.03, 23.53, 20.89, J = 10.5, 3.9 Hz, 4H), 18.85, 18.38, 11.88 1.47-1.34 (m, 1H), 1.30 (d, J = 6.5 Hz, 3H), 1.26-1.21 (m, 1H), 1.17 (s, 1H), 0.88 (t, J = 7.3 Hz, 3H) F137 — — ESIMS ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 627 1H), 8.26 (d, J = 5.4 Hz, 172.70, 170.27, ([M + H]⁺) 1H), 7.43-7.27 (m, 5H), 162.98, 7.08 (td, J = 8.7, 6.7 Hz, 1H), 162.96-159.98 (m), 6.93 (d, J = 5.4 Hz, 1H), 161.13 (dd, J = 248.8, 13.1 Hz), 6.81-6.72 (m, 2H), 5.73 (s, 2H), 160.25, 145.77, 4.98 (dq, J = 9.2, 6.4 Hz, 1H), 143.92, 142.40, 4.81 (d, J = 10.8 Hz, 1H), 137.82, 131.60 (dd, J = 9.2, 4.64 (d, J = 10.9 Hz, 1H), 4.60 (dt, 6.7 Hz), 128.53, J = 10.9, 7.3 Hz, 1H), 3.89 (s, 127.91, 127.67, 3H), 3.40 (t, J = 9.0 Hz, 1H), 123.17 (dd, J = 16.0, 3.8 Hz), 3.12-2.93 (m, 1H), 2.50 (dd, 111.06 (dd, J = 20.7, J = 13.6, 11.5 Hz, 1H), 3.9 Hz), 109.64, 2.39-2.27 (m, 1H), 2.06 (s, 3H), 104.33-103.29 (m), 1.94 (ddq, J = 12.2, 8.0, 3.9 Hz, 89.49, 83.96, 75.39, 1H), 1.70-1.57 (m, 2H), 74.97, 56.20, 51.79, 1.52 (d, J = 6.4 Hz, 3H), 44.52, 33.59, 29.35, 1.49-1.38 (m, 1H), 1.30-1.17 (m, 27.15, 20.89, 18.89, 1H), 1.01-0.90 (m, 1H) 18.27 ¹⁹F NMR (CDCl₃) δ −113.32 (d, J = 6.4 Hz), −113.57 (d, J = 6.7 Hz) F138 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz, 172.69, 170.29, [M + H]⁺ 1H), 7.36-7.28 (m, 2H), 163.00, 160.27, calcd for 7.05-6.91 (m, 4H), 158.93, 145.77, C₂₇H₃₃O₈N₂F₂, 6.03-5.67 (m, 1H), 5.75 (s, 2H), 144.00, 142.31, 551.2199; 5.11 (dq, J = 9.1, 6.5 Hz, 1H), 129.84, 121.56, found, 4.72-4.56 (m, 1H), 4.24 (t, J = 8.7 Hz, 116.75, 115.26, 551.2202 1H), 3.92 (s, 3H), 109.65, 89.51, 80.58, 2.43 (dt, J = 12.9, 6.6 Hz, 1H), 74.49, 56.20, 51.91, 2.09 (s, 1H), 2.07 (s, 3H), 37.61, 35.77, 33.36, 2.06-1.95 (m, 1H), 1.94-1.75 (m, 29.42, 20.88, 19.32, 3H), 1.73-1.62 (m, 1H), 18.26 1.41 (q, J = 11.3 Hz, 1H), 1.31 (d, J = 6.5 Hz, 3H), 1.29-1.24 (m, 1H) F139 — — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 625 1H), 8.25 (d, J = 5.3 Hz, 172.62, 170.16, ([M + H]⁺) 1H), 7.09 (d, J = 7.8 Hz, 162.87, 160.15, 2H), 7.03 (d, J = 8.1 Hz, 2H), 145.66, 143.82, 6.93 (d, J = 5.4 Hz, 1H), 142.30, 137.20, 5.72 (s, 2H), 4.89 (dq, J = 9.2, 6.4 Hz, 135.37, 128.99, 1H), 4.56 (dt, J = 10.9, 7.4 Hz, 128.55, 127.06 (q, J = 276.1 Hz), 1H), 3.88 (s, 3H), 3.79 (dt, 109.53, J = 8.9, 6.1 Hz, 1H), 3.59 (dt, J = 8.8, 89.37, 84.16, 74.79, 6.2 Hz, 1H), 3.17 (t, J = 9.0 Hz, 71.57, 56.08, 51.68, 1H), 2.96 (dd, J = 13.3, 45.79, 36.39, 33.52, 3.4 Hz, 1H), 30.69 (q, J = 29.1 Hz), 2.41-2.12 (m, 7H), 2.05 (s, 3H), 26.57, 22.98 (q, J = 2.9 Hz), 1.91-1.76 (m, 3H), 1.68-1.36 (m, 20.90, 20.76, 6H), 1.28-1.12 (m, 1H), 18.71, 18.01 0.92-0.79 (m, 1H) ¹⁹F NMR (CDCl₃) δ −66.35 140 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.13 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.07 (d, J = 5.4 Hz, 172.75, 170.21, [M + H]⁺ 1H), 6.76 (d, J = 5.4 Hz, 162.92, 160.21, calcd for 1H), 5.53 (s, 2H), 4.69 (dt, J = 9.1, 145.73, 143.86, C₂₉H₄₃O₉N₂, 6.4 Hz, 1H), 4.37 (dt, J = 10.7, 142.41, 109.60, 89.45, 563.2963; 7.5 Hz, 1H), 3.71 (s, 3H), 83.98, 78.32, 75.39, found, 3.26 (dt, J = 13.1, 6.7 Hz, 4H), 75.28, 69.04, 56.17, 563.2959 3.05 (dq, J = 6.5, 3.3 Hz, 2H), 51.80, 40.46, 33.60, 2.88 (t, J = 8.9 Hz, 1H), 30.63, 28.16, 20.84, 2.15 (dt, J = 13.2, 6.5 Hz, 1H), 19.00, 18.06, 11.07, 1.86 (s, 3H), 1.80 (dp, J = 13.0, 4.8, 10.63, 3.14, 2.98, 2.92, 4.0 Hz, 1H), 1.59-1.39 (m, 2.86 3H), 1.39-1.25 (m, 2H), 1.22 (d, J = 6.4 Hz, 3H), 1.13 (q, J = 11.5 Hz, 1H), 0.95-0.77 (m, 3H), 0.43-0.23 (m, 4H), 0.00 (dq, J = 10.1, 5.2, 4.5 Hz, 4H) F141 40-45 — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 655 1H), 8.25 (d, J = 5.3 Hz, 172.62, 170.17, ([M + H]⁺) 1H), 7.31-7.23 (m, 2H), 162.88, 161.27 (dd, J = 246.7, 7.23-7.07 (m, 4H), 6.93 (d, J = 5.4 Hz, 12.2 Hz), 1H), 6.85-6.72 (m, 161.05 (dd, J = 248.0, 2H), 5.73 (s, 2H), 4.91 (dq, J = 9.2, 12.2 Hz), 160.15, 6.4 Hz, 1H), 4.57 (dt, J = 10.9, 145.67, 143.83, 7.5 Hz, 1H), 3.89 (s, 3H), 142.33, 141.66, 3.78 (dt, J = 8.8, 6.3 Hz, 1H), 131.50 (dd, J = 9.3, 6.6 Hz), 3.57 (dt, J = 8.9, 6.5 Hz, 1H), 128.29, 128.24, 3.18 (t, J = 9.0 Hz, 1H), 125.79, 123.19 (dd, J = 16.0, 2.98 (d, J = 12.8 Hz, 1H), 2.73 (td, 3.8 Hz), J = 7.5, 4.0 Hz, 2H), 2.47 (dd, 110.96 (dd, J = 20.8, 3.7 Hz), J = 13.5, 11.5 Hz, 1H), 109.54, 2.31 (ddd, J = 13.2, 6.7, 4.9 Hz, 103.97-103.18 (m), 89.40, 1H), 2.06 (s, 3H), 83.99, 74.96, 72.86, 2.00-1.80 (m, 3H), 1.68-1.51 (m, 2H), 56.10, 51.68, 44.45, 1.49-1.36 (m, 4H), 33.51, 32.33, 31.87, 1.28-1.15 (m, 1H), 0.91 (ddt, J = 14.5, 29.30, 27.05, 20.79, 6.4, 3.0 Hz, 1H) 18.76, 18.04 ¹⁹F NMR (CDCl₃) δ −113.37 (d, J = 6.6 Hz), −113.58 (d, J = 7.5 Hz) F142 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.76, 170.26, [M + H]⁺ 1H), 7.39-7.19 (m, 2H), 162.96, 160.24, calcd for 6.98-6.92 (m, 2H), 158.86, 145.76, C₃₁H₄₁O₉N₂, 6.92-6.86 (m, 2H), 5.74 (s, 2H), 143.92, 142.44, 585.2807; 5.07-4.84 (m, 1H), 4.59 (dt, J = 10.7, 129.41, 120.59, found, 7.4 Hz, 1H), 114.48, 109.61, 89.51, 585.2816 4.16-3.96 (m, 2H), 3.90 (s, 3H), 83.95, 78.24, 75.25, 3.49 (dd, J = 9.6, 7.3 Hz, 1H), 66.18, 56.19, 51.83, 3.42 (dd, J = 9.6, 6.8 Hz, 1H), 40.33, 33.61, 30.34, 3.14 (t, J = 8.8 Hz, 1H), 28.17, 20.88, 19.10, 2.36 (dt, J = 13.2, 6.7 Hz, 1H), 18.10, 11.09, 3.16, 2.19 (ddd, J = 15.0, 5.8, 2.3 Hz, 2.94 1H), 2.07 (s, 3H), 1.90-1.75 (m, 2H), 1.69 (dq, J = 21.9, 7.6, 7.0 Hz, 2H), 1.62-1.50 (m, 1H), 1.44 (d, J = 6.4 Hz, 3H), 1.34 (q, J = 11.5 Hz, 1H), 1.07 (dt, J = 12.1, 5.9 Hz, 2H), 0.60-0.49 (m, 2H), 0.21 (q, J = 4.9 Hz, 2H) F143 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.42 (d, J = 6.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (dt, J = 5.0, 173.64, 170.23, [M + H]⁺ 2.6 Hz, 1H), 162.85, 160.26, calcd for 7.07-6.83 (m, 1H), 5.82-5.59 (m, 2H), 145.75, 143.93, C₂₁H₂₉O₂N₈, 5.10-4.89 (m, 1H), 142.43, 109.60, 89.53, 437.1918; 4.64-4.43 (m, 1H), 4.04-3.87 (m, 86.83, 73.26, 67.69, found, 3H), 3.80 (s, 1H), 3.69 (dq, J = 8.7, 56.18, 53.28, 39.69, 437.1929 5.3, 4.7 Hz, 1H), 3.42 (dd, 36.09, 35.75, 32.41, J = 8.2, 3.6 Hz, 1H), 2.38 (t, J = 11.9 Hz, 21.78, 20.85, 18.37 1H), 2.12-2.04 (m, 3H), 2.05-1.83 (m, 3H), 1.74 (d, J = 14.6 Hz, 1H), 1.64 (t, J = 12.7 Hz, 1H), 1.50 (d, J = 9.5 Hz, 2H), 1.46-1.32 (m, 4H) F144 76-80 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ m/z 631 1H), 8.22 (d, J = 5.4 Hz, 172.51, 170.12, ([M + H]⁺) 1H), 7.58 (dd, J = 1.9, 0.6 Hz, 162.84, 161.37 (dd, J = 246.6, 1H), 7.15 (dd, J = 3.4, 0.6 Hz, 11.6 Hz), 1H), 7.02 (td, J = 8.5, 6.4 Hz, 160.88 (dd, J = 247.6, 1H), 6.92 (d, J = 5.4 Hz, 11.5 Hz), 160.13, 1H), 6.73-6.62 (m, 2H), 158.06, 146.83, 6.50 (dd, J = 3.5, 1.7 Hz, 1H), 145.59, 143.86, 5.70 (s, 2H), 5.18 (t, J = 9.2 Hz, 143.79, 142.14, 1H), 5.09 (dq, J = 9.5, 6.3 Hz, 131.49 (dd, J = 9.5, 6.5 Hz), 1H), 4.60 (dt, J = 10.9, 7.4 Hz, 122.36 (dd, J = 15.7, 1H), 3.86 (s, 3H), 2.70 (dd, J = 13.9, 3.8 Hz), 118.50, 4.5 Hz, 1H), 2.49 (dd, J = 13.9, 111.88, 110.81 (dd, J = 21.0, 10.2 Hz, 1H), 3.7 Hz), 2.34 (ddt, J = 13.2, 7.4, 3.7 Hz, 109.55, 103.56 (t, J = 25.7 Hz), 1H), 2.18-2.07 (m, 1H), 89.32, 76.33, 2.03 (s, 3H), 1.73-1.51 (m, 3H), 72.97, 56.06, 51.59, 1.29 (d, J = 6.3 Hz, 3H), 42.51, 33.26, 29.97, 1.27-1.18 (m, 1H), 1.12-0.98 (m, 27.25, 20.72, 18.65, 1H) 17.38 ¹⁹F NMR (CDCl₃) δ −112.99 (d, J = 6.8 Hz), −113.49 (d, J = 6.9 Hz) F145 48-53 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 593 1H), 8.25 (d, J = 5.4 Hz, 172.33, 169.88, ([M + H]⁺) 1H), 7.11 (td, J = 8.5, 6.5 Hz, 162.58, 160.96 (dd, J = 246.6, 1H), 6.92 (d, J = 5.4 Hz, 12.1 Hz), 1H), 6.82-6.71 (m, 2H), 160.77 (dd, J = 247.7, 5.72 (s, 2H), 4.89 (dq, J = 9.2, 6.4 Hz, 11.9 Hz), 159.86, 1H), 4.57 (ddd, J = 10.9, 145.37, 143.54, 8.1, 7.0 Hz, 1H), 3.88 (s, 3H), 142.06, 131.51 3.54 (dd, J = 8.4, 6.2 Hz, 1H), −130.92 (m), 3.31 (dd, J = 8.4, 6.5 Hz, 1H), 122.97 (dd, J = 16.0, 3.8 Hz), 3.15 (t, J = 9.0 Hz, 1H), 110.65 (dd, J = 20.8, 3.04-2.93 (m, 1H), 2.46 (dd, J = 13.5, 3.9 Hz), 109.22, 11.6 Hz, 1H), 2.30 (dtd, J = 13.1, 103.94-102.92 (m), 6.6, 1.9 Hz, 1H), 89.12, 83.23, 80.04, 2.05 (s, 3H), 1.94-1.77 (m, 2H), 74.80, 55.80, 51.38, 1.66-1.51 (m, 2H), 44.35, 33.25, 28.85, 1.49-1.34 (m, 4H), 1.31-1.14 (m, 28.83, 26.71, 20.49, 2H), 0.95 (d, J = 6.7 Hz, 3H), 19.10, 19.07, 18.47, 0.94 (d, J = 6.7 Hz, 3H) 17.76 ¹⁹F NMR (CDCl₃) δ −113.49 (d, J = 6.7 Hz), −113.61 (d, J = 7.0 Hz) F146 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.84, 170.31, [M + H]⁺ 1H), 7.26 (s, 2H), 162.97, 159.33, calcd for 6.93 (ddd, J = 7.8, 5.4, 4.2 Hz, 4H), 145.75, 138.53, C₂H₃₃N₂O₈, 5.84-5.75 (m, 1H), 5.75 (s, 129.49, 121.09, 513.2231; 2H), 5.15 (dq, J = 9.1, 6.4 Hz, 116.19, 115.78, found, 1H), 5.04 (dt, J = 17.1, 1.3 Hz, 109.61, 99.97, 89.55, 513.2255 1H), 4.95 (d, J = 10.3 Hz, 1H), 80.48, 74.48, 56.19, 4.64 (ddd, J = 11.0, 7.9, 6.7 Hz, 51.95, 47.50, 33.61, 1H), 4.31 (t, J = 8.8 Hz, 31.11, 20.89, 19.77, 1H), 3.91 (s, 3H), 18.33 2.59-2.46 (m, 1H), 2.46-2.34 (m, 1H), 2.07 (s, 3H), 1.90 (td, J = 14.5, 6.7 Hz, 1H), 1.83-1.68 (m, 2H), 1.47-1.36 (m, 2H), 1.34 (d, J = 6.4 Hz, 3H) F147 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.41 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3383, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 176.24, 172.82, 2928, ([M]⁺) 1H), 7.33-7.23 (m, 2H), 162.94, 160.23, 1746, calcd for 7.00-6.89 (m, 4H), 159.72, 145.61, 1677, C₃₂H₄₄N₂O₈, 5.82-5.72 (m, 2H), 5.14-5.01 (m, 144.17, 142.09, 1493, 584.3098; 1H), 4.62 (ddd, J = 10.8, 8.0, 129.57, 120.95, 1207 found, 6.9 Hz, 1H), 4.26-4.16 (m, 115.50, 109.56, 89.88, 584.3108 1H), 3.89 (s, 3H), 2.55 (hept, J = 7.0 Hz, 81.64, 74.86, 56.14, 1H), 2.47-2.32 (m, 51.91, 43.23, 36.41, 1H), 1.94-1.31 (m, 7H), 33.86, 33.65, 28.27, 1.30 (d, J = 6.5 Hz, 3H), 27.88, 27.56, 23.04, 1.28-1.04 (m, 4H), 1.14 (d, J = 7.0 Hz, 22.06, 18.94, 18.68, 6H), 0.80 (d, J = 6.6 Hz, 18.40 3H), 0.79 (d, J = 6.6 Hz, 3H) F148 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.39 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 176.21, 172.86, 2925, ([M]⁺) 1H), 6.94 (d, J = 5.3 Hz, 162.90, 160.21, 1743, calcd for 1H), 5.82-5.72 (m, 2H), 145.60, 144.11, 1677, C₃₀H₄₈N₂O₈, 4.94-4.81 (m, 1H), 4.57 (ddd, J = 10.7, 142.15, 109.51, 89.88, 1504, 564.3411; 8.1, 7.0 Hz, 1H), 3.89 (s, 84.32, 80.43, 75.43, 1209 found, 3H), 3.46 (dd, J = 8.3, 6.3 Hz, 56.12, 51.86, 43.55, 564.3413 1H), 3.27 (dd, J = 8.4, 6.5 Hz, 36.55, 33.84, 33.70, 1H), 3.07-2.94 (m, 1H), 29.18, 28.11, 28.04, 2.55 (hept, J = 7.0 Hz, 1H), 27.56, 22.98, 22.28 2.42-2.27 (m, 1H), 1.94-1.43 (m, 19.52, 19.46, 18.86, 7H), 1.41 (d, J = 6.4 Hz, 3H), 18.67, 18.17 1.38-0.95 (m, 5H), 1.14 (d, J = 7.0 Hz, 6H), 0.95-0.81 (m, 12H) F149 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 176.22, 172.83, 2927, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.91, 160.22, 1745, calcd for 1H), 5.81-5.72 (m, 2H), 145.61, 144.12, 1678, C₃₀H₄₆N₂O₈, 4.96-4.82 (m, 1H), 4.57 (ddd, J = 10.7, 142.15, 109.51, 89.88, 1505, 562.3254; 8.1, 7.0 Hz, 1H), 3.89 (s, 84.36, 78.64, 75.39, 1374, found, 3H), 3.58-3.31 (m, 2H), 56.13, 51.83, 43.60, 1210 562.3262 3.09-2.97 (m, 1H), 2.55 (hept, J = 7.0 Hz, 36.44, 33.85, 33.72, 1H), 2.40-2.29 (m, 28.08, 27.35, 23.03, 1H), 1.86-1.45 (m, 6H), 22.22, 18.75, 18.67, 1.42 (d, J = 6.4 Hz, 3H), 18.11, 11.13, 3.08, 1.38-0.93 (m, 6H), 1.14 (d, J = 7.0 Hz, 3.01 6H), 0.90 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.50 (m, 2H), 0.27-0.15 (m, 2H) F150 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3385, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 176.24, 172.82, 2950, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.93, 160.24, 1746, calcd for 1H), 5.81-5.72 (m, 2H), 145.61, 144.16, 1679, C₃₀H₄₅F₃N₂O₈, 4.93-4.81 (m, 1H), 4.57 (ddd, J = 10.7, 142.13, 127.17 (q, J = 276.1 Hz), 1506, 618.3128; 8.1, 7.0 Hz, 1H), 3.89 (s, 109.52, 1377, found, 3H), 3.80-3.66 (m, 1H), 89.90, 84.85, 75.02, 1253 618.3154 3.64-3.50 (m, 1H), 3.09-2.98 (m, 71.55, 56.13, 51.85, 1H), 2.55 (hept, J = 7.0 Hz, 43.48, 36.49, 33.86, 1H), 2.40-2.28 (m, 1H), 33.66, 30.82 (q, J = 29.0 Hz), 2.28-2.11 (m, 2H), 1.88-1.27 (m, 28.20, 28.09, 9H), 1.40 (d, J = 6.4 Hz, 3H), 27.47, 23.06 (dd, J = 6.5, 1.27-0.92 (m, 4H), 1.14 (d, J = 7.0 Hz, 3.4 Hz), 22.97, 6H), 0.92-0.83 (m, 22.18, 18.84, 18.67, 6H) 18.14 ¹⁹F NMR (CDCl₃) δ −66.43 F151 122-124 — ESIMS ¹H NMR (CDCl₃) δ 8.36 (d, J = 7.2 Hz, ¹³C NMR (CDCl₃) δ m/z 585.5 1H), 8.31 (d, J = 5.4 Hz, 176.39, 170.64, ([M + H]⁺) 1H), 7.31-7.24 (m, 2H), 162.92, 160.31, 7.21-7.15 (m, 3H), 6.97 (d, J = 5.4 Hz, 145.61, 144.44, 1H), 5.76 (s, 2H), 142.06, 140.87, 5.04-4.92 (m, 1H), 4.60 (dd, 128.87, 128.36, J = 7.3, 3.8 Hz, 1H), 3.90 (s, 125.91, 109.53, 89.99, 3H), 3.54 (dd, J = 8.3, 6.3 Hz, 84.01, 80.55, 75.32, 1H), 3.39-3.30 (m, 1H), 56.17, 52.13, 45.78, 3.20-3.10 (m, 2H), 37.01, 33.87, 31.97, 2.62-2.49 (m, 1H), 2.40-2.28 (m, 1H), 29.26, 26.94, 19.55, 2.00-1.80 (m, 3H), 19.50, 18.69, 18.16, 1.75-1.62 (m, 1H), 1.56 (dd, J = 13.8, 17.44 7.4 Hz, 1H), 1.48-1.41 (m, 4H), 1.26 (dd, J = 8.1, 6.2 Hz, 1H), 1.22-1.17 (m, 1H), 1.15 (dd, J = 4.9, 2.1 Hz, 6H), 0.99-0.93 (m, 7H), 0.93-0.86 (m, 1H) F152 — — ESIMS ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (75 MHz, m/z 583.6 1H), 8.25 (d, J = 5.4 Hz, CDCl₃) δ 176.36, ([M + H]⁺) 1H), 7.35-7.24 (m, 2H), 172.91, 163.12, 7.22-7.13 (m, 3H), 6.93 (d, J = 5.4 Hz, 160.42, 145.79, 1H), 5.82-5.68 (m, 144.30, 142.34, 2H), 4.93 (dq, J = 9.1, 6.4 Hz, 140.94, 129.07, 1H), 4.58 (ddd, J = 10.8, 8.1, 128.54, 126.08, 7.0 Hz, 1H), 3.88 (s, 3H), 109.74, 90.05, 84.04, 3.59 (dd, J = 9.6, 7.0 Hz, 1H), 78.91, 75.41, 56.33, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 54.04, 51.98, 46.25, 3.26-3.07 (m, 2H), 2.54 (p, J = 7.0 Hz, 37.12, 34.06, 33.91, 1H), 2.43-2.23 (m, 2H), 29.49, 26.85, 19.02, 1.97-1.79 (m, 1H), 18.87, 18.32, 11.39, 1.69-1.51 (m, 2H), 1.49-1.38 (m, 3.35, 3.21 overlapping, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.22-1.05 (m, 2H), 1.14 (d, overlapping, J = 7.0 Hz, 6H), 0.95-0.80 (m, 1H), 0.65-0.53 (m, 2H), 0.33-0.19 (m, 2H) F153 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 172.72, 169.43, [M + H]⁺ 1H), 7.35-7.23 (m, 2H), 162.36, 159.77, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.44, 146.77, C₃₂H₄₃N₂O₈, 6.97-6.89 (m, 3H), 5.07 (dq, J = 9.1, 141.48, 137.34, 583.3014; 6.5 Hz, 1H), 4.60 (ddd, J = 10.9, 129.58, 120.93, found, 8.3, 6.9 Hz, 1H), 115.56, 109.80, 81.67, 583.3013 4.16 (t, J = 8.7 Hz, 1H), 3.90 (s, 74.88, 67.71, 67.59, 3H), 3.81 (t, J = 6.6 Hz, 2H), 58.87, 58.79, 56.33, 3.69 (dt, J = 9.2, 5.7 Hz, 1H), 51.66, 42.02, 37.27, 3.41 (s, 3H), 2.99 (t, J = 6.6 Hz, 36.85, 34.62, 33.87, 2H), 2.63 (t, J = 6.2 Hz, 33.66, 31.77, 27.61, 1H), 2.37 (dt, J = 13.3, 6.6 Hz, 25.05, 19.07, 18.38 1H), 1.83 (dh, J = 16.6, 4.8, 4.2 Hz, 3H), 1.77-1.35 (m, 9H), 1.28 (d, J = 6.5 Hz, 3H), 1.18-1.07 (m, 1H), 0.98 (ddq, J = 15.6, 12.5, 7.9 Hz, 2H) F154 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 8.2 Hz, Film) (m/z) 1H), 8.27 (d, J = 5.3 Hz, 3381, ([M]⁺) 1H), 6.93 (d, J = 5.4 Hz, 2942, calcd for 1H), 5.81-5.61 (m, 2H), 1745, C₃₁H₄₆N₂O₈, 4.89 (dd, J = 9.2, 6.3 Hz, 1H), 1678, 574.3254; 4.57 (dt, J = 11.0, 7.5 Hz, 1H), 1506, found, 3.89 (s, 3H), 3.50 (dd, J = 9.6, 7.0 Hz, 974 674.3262 1H), 3.36 (dd, J = 9.6, 6.9 Hz, 1H), 3.01 (t, J = 9.0 Hz, 1H), 2.54 (p, J = 7.0 Hz, 1H), 2.36 (dd, J = 13.1, 6.8 Hz, 1H), 1.92-1.43 (m, 15H), 1.42 (d, J = 6.5 Hz, 2H), 1.35-1.19 (m, 2H), 1.14 (d, J = 7.0 Hz, 3H), 1.17-0.92 (m, 5H), 0.62-0.48 (m, 2H), 0.29-0.17 (m, 2H) F155 HRMS-ESI ¹H NMR (CDCl₃) δ 8.42 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 176.26, 172.85, ([M]⁺) 1H), 7.33-7.23 (m, 2H), 162.94, 160.24, calcd for 7.01-6.89 (m, 4H), 159.69, 145.62, C₂₈H₃₆N₂O₈, 5.83-5.73 (m, 2H), 5.10 (dq, J = 9.1, 144.19, 142.08, 528.2472; 6.4 Hz, 1H), 4.68-4.55 (m, 129.59, 120.99, found, 1H), 4.17 (t, J = 8.8 Hz, 1H), 115.49, 109.55, 89.90, 528.2485 3.89 (s, 3H), 2.55 (hept, J = 7.0 Hz, 82.30, 74.68, 56.14, 1H), 2.40 (dt, J = 13.0, 51.95, 37.67, 33.86, 6.6 Hz, 1H), 2.01-1.85 (m, 33.63, 32.38, 19.27, 1H), 1.70 (dq, J = 16.8, 5.4, 18.69, 18.31, 17.77 4.7 Hz, 3H), 1.40 (dt, J = 13.5, 10.6 Hz, 1H), 1.31 (d, J = 6.4 Hz, 3H), 1.29-1.22 (m, 1H), 1.15 (d, J = 7.0 Hz, 6H), 1.01 (d, J = 6.9 Hz, 3H) F156 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.19 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.06 (d, J = 5.4 Hz, 176.13, 172.72, [M + H]⁺ 1H), 6.75 (d, J = 5.4 Hz, 162.87, 160.17, calcd for 1H), 5.66-5.50 (m, 2H), 145.59, 144.05, C₃₁H₄₇O₉N₂, 4.70 (dt, J = 9.1, 6.4 Hz, 1H), 142.05, 109.54, 89.79, 591.3276; 4.37 (dt, J = 10.7, 7.4 Hz, 1H), 83.98, 78.29, 75.36, found, 3.69 (s, 3H), 3.34-3.18 (m, 4H), 75.24, 69.01, 56.11, 591.3280 3.15-3.00 (m, 2H), 2.88 (t, J = 8.8 Hz, 51.78, 40.43, 33.79, 1H), 2.34 (p, J = 7.0 Hz, 33.59, 30.63, 28.17, 1H), 2.15 (dt, J = 13.1, 6.5 Hz, 19.01, 18.62, 18.04, 1H), 1.81 (dp, J = 12.9, 11.06, 10.61, 3.12, 4.8, 4.0 Hz, 1H), 1.48 (td, J = 18.9, 2.96, 2.90, 2.85 14.6, 5.7 Hz, 3H), 1.40-1.27 (m, 2H), 1.22 (d, J = 6.4 Hz, 3H), 1.13 (q, J = 11.3 Hz, 1H), 0.94 (d, J = 7.0 Hz, 6H), 0.91-0.75 (m, 3H), 0.44-0.26 (m, 4H), 0.10-−0.06 (m, 4H) F157 68-72 ESIMS ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 659 1H), 8.22 (d, J = 5.3 Hz, 176.11, 172.53, ([M + H]⁺) 1H), 7.59 (dd, J = 1.7, 0.8 Hz, 162.83, 161.40 (dd, J = 246.3, 1H), 7.15 (dd, J = 3.5, 0.8 Hz, 11.4 Hz,) 1H), 7.03 (td, J = 8.5, 6.4 Hz, 160.91 (dd, J = 247.6, 1H), 6.91 (d, J = 5.4 Hz, 11.4 Hz), 160.13, 1H), 6.74-6.63 (m, 2H), 158.08, 146.84, 6.50 (dd, J = 3.5, 1.7 Hz, 1H), 145.47, 144.12, 5.77-5.70 (m, 2H), 5.19 (t, J = 9.2 Hz, 143.82, 141.83, 1H), 4.61 (dt, J = 10.9, 7.5 Hz, 131.51 (dd, J = 9.3, 6.5 Hz), 1H), 3.85 (s, 3H), 122.39 (dd, J = 15.8, 2.71 (dd, J = 13.9, 4.5 Hz, 1H), 3.7 Hz), 118.52, 2.57-2.46 (m, 2H), 2.35 (ddt, 111.90, 110.83 (dd, J = 21.0, J = 13.2, 7.7, 3.3 Hz, 1H), 3.6 Hz), 2.18-2.07 (m, 1H), 1.74-1.52 (m, 109.50, 103.58 (t, J = 25.7 Hz), 3H), 1.34-1.18 (m, 5H), 89.72, 76.37, 1.11 (d, J = 7.0 Hz, 6H) 72.98, 56.02, 51.61, 42.53, 33.72, 33.31, 30.00, 27.28, 18.68, 18.55, 17.41 ¹⁹F NMR (CDCl₃) δ −113.00 (d, J = 7.1 Hz), −113.49 (d, J = 6.7 Hz) F158 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 2926, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.79, 170.04, 1746, ([M]⁺) 1H), 7.35-7.23 (m, 2H), 162.91, 160.16, 1678, calcd for 6.99-6.91 (m, 4H), 5.82 (s, 159.70, 145.80, 1494, C₃₂H₄₄N₂O₉, 2H), 5.14-5.01 (m, 1H), 143.89, 142.25, 1208, 600.3047; 4.67-4.54 (m, 1H), 4.25-4.17 (m, 129.57, 120.95, 1098 found, 1H), 4.10 (s, 2H), 3.90 (s, 3H), 115.48, 109.73, 89.50, 600.3070 3.59 (q, J = 7.0 Hz, 2H), 81.62, 74.86, 67.78, 2.47-2.31 (m, 1H), 1.98-1.31 (m, 67.16, 56.23, 51.90, 7H), 1.30 (d, J = 6.4 Hz, 3H), 43.20, 36.39, 33.61, 1.27-1.03 (m, 4H), 1.23 (t, J = 7.0 Hz, 28.26, 27.87, 27.58, 3H), 0.80 (d, J = 6.7 Hz, 23.03, 22.05, 18.94, 3H), 0.79 (d, J = 6.6 Hz, 18.39, 15.01 3H) F159 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 2954 (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.83, 170.03, 1744, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.86, 160.14, 1679, calcd for 1H), 5.82 (s, 2H), 145.78, 143.85, 1506, C₃₀H₄₈N₂O₉, 4.94-4.81 (m, 1H), 4.63-4.49 (m, 1H), 142.34, 109.66, 89.53, 1210, 580.3360; 4.10 (s, 2H), 3.90 (s, 3H), 84.31, 80.43, 75.45, 1096 found, 3.59 (q, J = 7.0 Hz, 2H), 3.46 (dd, J = 8.4, 67.78, 67.16, 56.20, 580.3379 6.3 Hz, 1H), 3.27 (dd, J = 8.4, 51.85, 43.53, 36.55, 6.5 Hz, 1H), 33.68, 29.18, 28.11, 3.06-2.96 (m, 1H), 2.41-2.26 (m, 1H), 28.03, 27.58, 22.97, 1.92-1.42 (m, 7H), 1.41 (d, J = 6.4 Hz, 22.28, 19.51, 19.46, 3H), 1.38-0.95 (m, 18.85, 18.17, 15.00 5H), 1.23 (t, J = 7.0 Hz, 3H), 0.95-0.82 (m, 12H) F160 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.27 (d, J = 5.5 Hz, 172.81, 170.04, 2948, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.88, 160.15, 1741, calcd for 1H), 5.82 (s, 2H), 145.80, 143.85, 1676, C₃₀H₄₆N₂O₉, 4.95-4.82 (m, 1H), 4.55 (ddd, J = 10.7, 142.34, 109.68, 89.53, 1504, 578.3203; 8.2, 7.0 Hz, 1H), 4.10 (s, 2H), 84.36, 78.63, 75.41, 1374, found, 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 67.78, 67.17, 56.21, 1209 578.3206 2H), 3.51 (dd J = 9.7, 7.0 Hz, 51.83, 43.58, 36.43, 1H), 3.38 (dd J = 9.7, 6.9 Hz, 33.69, 28.07, 27.37, 1H), 3.09-2.97 (m, 1H), 23.03, 22.21, 18.75, 2.40-2.27 (m, 1H), 18.11, 15.00, 11.13 1.84-1.45 (m, 6H), 1.42 (d, J = 6.4 Hz, 3.08, 3.01 3H), 1.38-0.92 (m, 6H), 1.23 (t, J = 7.0 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.50 (m, 2H), 0.28-0.16 (m, 2H) F161 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.84, 170.04, 2933, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.88, 160.16, 1742, calcd for 1H), 5.82 (s, 2H), 145.78, 143.88, 1677, C₂₉H₄₆N₂O₉, 4.93-4.81 (m, 1H), 4.56 (ddd, J = 10.8, 142.36, 109.66, 89.56, 1504, 566.3203; 8.1, 7.0 Hz, 1H), 4.10 (s, 2H), 84.58, 75.42, 67.79, 1374, found, 3.90 (s, 3H), 3.69-3.57 (m, 67.17, 56.21, 51.85, 1128 566.3237 1H), 3.59 (q, J = 7.0 Hz, 2H), 43.52, 36.51, 33.71, 3.51-3.41 (m, 1H), 28.10, 27.52, 23.54, 3.07-2.98 (m, 1H), 2.41-2.27 (m, 23.02, 22.22, 18.82, 1H), 1.82-1.27 (m, 9H) 18.12, 15.00, 10.70 1.42 (d, J = 6.4 Hz, 3H), 1.27-0.95 (m, 4H), 1.23 (t, J = 7.0 Hz, 3H), 0.94 (t, J = 7.4 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F162 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3377, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.80, 170.05, 2950, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.90, 160.17, 1744, calcd for 1H), 5.82 (s, 2H), 145.79, 143.90, 1678, C₃₀H₄₅F₃N₂O₉, 4.93-4.81 (m, 1H), 4.56 (ddd, J = 10.7, 142.31, 127.17 (q, J = 275.9 Hz), 1505, 634.3077; 8.0, 6.9 Hz, 1H), 4.10 (s, 2H), 109.69, 1314, found, 3.90 (s, 3H), 3.79-3.69 (m, 89.55, 84.85, 75.05, 1130 634.3089 1H), 3.63-3.52 (m, 1H), 71.55, 67.79, 67.18, 3.59 (q, J = 7.0 Hz, 2H), 56.21, 51.84, 43.46, 3.09-2.98 (m, 1H), 2.40-2.28 (m, 36.48, 33.64, 30.82 (q, 1H), 2.28-2.12 (m, 2H), J = 29.1 Hz), 28.20, 1.89-1.27 (m, 9H), 1.40 (d, J = 6.4 Hz, 28.09, 27.48, 23.06 (q, 3H), 1.27-0.94 (m, 4H), J = 3.0 Hz), 22.96, 1.23 (t, J = 7.0 Hz, 3H), 22.17, 18.84, 18.14, 0.93-0.83 (m, 6H) 15.00 ¹⁹F NMR (CDCl₃) δ −66.44 F163 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.77, 170.03, 2941, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.87, 160.15, 1743, calcd for 1H), 5.82 (s, 2H), 145.78, 143.86, 1678, C₂₇H₄₂N₂O₉, 4.92-4.80 (m, 1H), 4.62-4.50 (m, 1H), 142.32, 109.68, 89.51, 1504, 538.2890; 4.10 (s, 2H), 3.90 (s, 3H), 86.41, 75.14, 67.77, 1374, found, 3.59 (q, J = 7.0 Hz, 2H), 3.50 (s, 67.15, 61.18, 56.21, 1210 538.2903 3H), 2.99-2.89 (m, 1H), 51.80, 43.53, 36.47, 2.41-2.26 (m, 1H), 1.83-1.27 (m, 33.67, 28.24, 28.14, 7H), 1.43 (d, J = 6.4 Hz, 3H), 27.26, 23.07, 22.16, 1.27-0.92 (m, 4H), 1.23 (t, J = 7.0 Hz, 18.75, 18.05, 14.99 3H), 0.90 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F164 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3381, (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.66, 170.01, 2938, ([M]⁺) 1H), 7.17-7.09 (m, 2H), 162.89, 161.26 (d, J = 243.6 Hz), 1742, calcd for 7.02-6.91 (m, 3H), 5.81 (s, 160.14, 1677, C₃₂H₄₁FN₂O₉, 2H), 4.99-4.84 (m, 1H), 145.79, 143.83, 1507, 616.2796; 4.56 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.25, 136.32 (d, J = 3.2 Hz), 1314, found, 1H), 4.09 (s, 2H), 3.90 (s, 3H), 130.14 (d, J = 7.7 Hz), 1218 616.2815 3.64-3.53 (m, 3H), 3.45 (dd, 115.10 (d, J = 21.0 Hz), J = 9.7, 6.8 Hz, 1H), 3.17 (t, J = 9.0 Hz, 109.71, 1H), 3.14-3.05 (m, 89.48, 83.72, 78.75, 1H), 2.37-2.23 (m, 2H), 75.18, 67.76, 67.14, 1.89-1.77 (m, 1H), 1.63-1.50 (m, 56.21, 51.73, 46.13, 2H), 1.47-1.34 (m, 1H), 36.04, 33.60, 26.62, 1.46 (d, J = 6.5 Hz, 3H), 18.77, 18.08, 14.99, 1.32-1.05 (m, 2H), 1.22 (t, J = 7.0 Hz, 11.16, 3.13, 2.99 3H), 0.95-0.80 (m, 1H), ¹⁹F NMR (CDCl₃) δ −117.49 0.65-0.52 (m, 2H), 0.31-0.19 (m, 2H) F165 68-70 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.67, 170.04, 2938, ([M]⁺) 1H), 7.35-7.25 (m, 2H), 162.92, 161.30 (d, J = 243.7 Hz), 1744, calcd for 7.13-6.87 (m, 8H), 5.82 (s, 160.17, 1676, C₃₄H₃₉FN₂O₉, 2H), 5.18-5.05 (m, 1H), 159.55, 145.80, 1507, 638.2640; 4.62 (ddd, J = 11.0, 8.1, 6.9 Hz, 143.91, 142.21, 1206 found, 1H), 4.38-4.29 (m, 1H), 135.84 (d, J = 3.1 Hz), 638.2663 4.10 (s, 2H), 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 130.10 (d, J = 7.7 Hz), 2H), 3.03-2.91 (m, 129.72, 121.25, 1H), 2.42-2.28 (m, 2H), 115.46, 115.11 (d, J = 21.1 Hz), 2.12-1.99 (m, 1H), 1.73-1.61 (m, 109.74, 2H), 1.61-1.46 (m, 1H), 89.50, 80.99, 74.62, 1.35 (d, J = 6.5 Hz, 3H), 67.79, 67.16, 56.22, 1.30-1.23 (m, 1H), 1.22 (t, J = 7.0 Hz, 51.82, 45.71, 36.11, 3H), 1.11-0.97 (m, 1H) 33.55, 26.81, 18.95, 18.35, 15.00 ¹⁹F NMR (CDCl₃) δ −117.34 F166 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3377, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 172.69, 170.04, 2939, ([M]⁺) 1H), 7.18-7.06 (m, 2H), 162.91, 161.30 (d, J = 243.6 Hz), 1743, calcd for 7.03-6.90 (m, 3H), 160.17, 1676, C₃₁H₃₉FN₂O₉, 6.06-5.84 (m, 1H), 5.82 (s, 2H), 145.80, 143.89, 1507, 602.2640; 5.33 (dq, J = 17.2, 1.6 Hz, 142.27, 136.26 (d, J = 3.3 Hz), 1220 found, 1H), 5.21 (dq, J = 10.4, 1.3 Hz, 134.30, 602.2648 1H), 4.98-4.87 (m, 1H), 130.14 (d, J = 7.7 Hz), 4.57 (ddd, J = 10.9, 8.1, 7.0 Hz, 117.15, 115.12 (d, J = 21.1 Hz), 1H), 4.29 (ddt, J = 12.3, 109.70, 5.5, 1.4 Hz, 1H), 89.53, 84.16, 75.05, 4.16-4.08 (m, 1H), 4.09 (s, 2H), 3.90 (s, 74.70, 67.80, 67.18, 3H), 3.59 (q, J = 7.0 Hz, 2H), 56.22, 51.76, 45.97, 3.30-3.18 (m, 1H), 36.11, 33.63, 26.63, 3.12-3.01 (m, 1H), 2.41-2.24 (m, 18.82, 18.16, 15.01 2H), 1.89-1.75 (m, 1H), ¹⁹F NMR (CDCl₃) δ −117.46 1.63-1.51 (m, 2H), 1.47 (d, J = 6.4 Hz, 3H), 1.46-1.36 (m, 1H), 1.28-1.14 (m, 1H), 1.23 (t, J = 7.0 Hz, 3H), 0.97-0.81 (m, 1H) F167 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.69, 170.03, ([M]⁺) 1H), 7.17-7.07 (m, 2H), 162.89, 161.27 (d, J = 243.6 Hz), calcd for 7.02-6.90 (m, 3H), 5.81 (s, 160.15, C₃₁H₄₁FN₂O₉, 2H), 4.98-4.83 (m, 1H), 145.80, 143.86, 604.2796; 4.57 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.27, 136.39 (d, J = 3.2 Hz), found, 1H), 4.09 (s, 2H), 3.90 (s, 3H), 130.13 (d, J = 7.7 Hz), 604.2800 3.73 (dt, J = 8.6, 6.5 Hz, 1H), 115.09 (d, J = 21.0 Hz), 3.59 (q, J = 7.0 Hz, 2H), 109.70, 3.52 (dt, J = 8.7, 6.7 Hz, 1H), 89.51, 83.92, 75.62, 3.20-3.11 (m, 1H), 3.11-3.01 (m, 75.21, 67.78, 67.16, 1H), 2.41-2.23 (m, 2H), 56.21, 51.75, 46.15, 1.87-1.72 (m, 1H), 1.71-1.51 (m, 36.00, 33.63, 26.63, 4H), 1.46 (d, J = 6.5 Hz, 3H), 23.58, 18.81, 18.09, 1.46-1.35 (m, 1H), 15.00, 10.72 1.30-1.14 (m, 1H), 1.23 (t, J = 7.0 Hz, ¹⁹F NMR (CDCl₃) δ −117.52 3H), 0.98 (t, J = 7.4 Hz, 3H), 0.94-0.79 (m, 1H) F168 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 172.70, 170.05, 2956, ([M]⁺) 1H), 7.17-7.06 (m, 2H), 162.90, 161.28 (d, J = 243.6 Hz), 1742, calcd for 7.03-6.89 (m, 3H), 5.82 (s, 160.16, 1677, C₃₂H₄₃FN₂O₉, 2H), 4.98-4.83 (m, 1H), 145.80, 143.89, 1507, 618.2953; 4.57 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.29, 136.43 (d, J = 3.2 Hz), 1375, found, 1H), 4.09 (s, 2H), 3.90 (s, 3H), 130.13 (d, J = 7.7 Hz), 1220 618.2960 3.59 (q, J = 7.0 Hz, 2H), 115.11 (d, J = 21.1 Hz), 3.56 (dd, J = 8.4, 6.3 Hz, 1H), 109.69, 3.33 (dd, J = 8.4, 6.5 Hz, 1H), 89.54, 83.66, 80.69, 3.18-3.10 (m, 1H), 3.10-3.00 (m, 75.25, 67.79, 67.18, 1H), 2.39-2.23 (m, 2H), 56.22, 51.76, 46.29, 1.97-1.73 (m, 2H), 1.63-1.51 (m, 35.91, 33.65, 29.27, 2H), 1.45 (d, J = 6.4 Hz, 3H), 26.59, 19.53, 19.49, 1.45-1.33 (m, 1H), 18.85, 18.17, 15.01 1.29-1.14 (m, 1H), 1.23 (t, J = 7.0 Hz, ¹⁹F NMR (CDCl₃) δ −117.52 3H), 0.97 (d, J = 6.7 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 0.93-0.80 (m, 1H) F169 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.56, 170.04, 2940, ([M]⁺) 1H), 7.18-7.05 (m, 2H), 162.92, 161.35 (d, J = 243.8 Hz), 1745, calcd for 7.03-6.90 (m, 3H), 5.87 (tt, J = 55.1, 160.17, 1678, C₃₀H₃₇F₃N₂O_(9,) 4.0 Hz, 1H), 5.81 (s, 145.81, 143.89, 1508, 626.2451; 2H), 5.00-4.87 (m, 1H), 142.19, 135.85 (d, J = 3.2 Hz), 1220 found, 4.56 (ddd, J = 10.9, 8.1, 7.0 Hz, 130.14 (d, J = 7.8 Hz), 626.2455 1H), 4.09 (s, 2H), 115.19 (d, J = 21.1 Hz), 4.06-3.91 (m, 1H), 3.90 (s, 3H), 113.88 (t, J = 241.2 Hz), 3.87-3.71 (m, 1H), 3.59 (q, J = 7.0 Hz, 109.75, 2H), 3.31-3.22 (m, 1H), 89.49, 85.53, 74.42, 3.10-2.99 (m, 1H), 72.59 (t, J = 27.6 Hz), 2.44-2.23 (m, 2H), 1.92-1.76 (m, 67.78, 67.16, 56.22, 1H), 1.68-1.36 (m, 3H), 51.72, 45.79, 35.92, 1.47 (d, J = 6.5 Hz, 3H), 33.50, 26.59, 18.86, 1.30-1.15 (m, 1H), 1.23 (t, J = 7.0 Hz, 18.14, 15.00 3H), 0.96-0.81 (m, 1H) ¹⁹F NMR (CDCl₃) δ −117.21, −125.47 (d, J = 9.4 Hz, 2F) F170 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.26 (d, J = 5.4 Hz, 176.11, 172.70, 2943, ([M]⁺) 1H), 7.12-7.02 (m, 2H), 170.06, 162.89, 1733, calcd for 7.01-6.91 (m, 3H), 5.81 (s, 161.36 (d, J = 244.0 Hz), 1678, C₃₄H₄₃FN₂O₁₀, 2H), 5.10-4.97 (m, 2H), 160.17, 145.75, 1508, 658.2902; 4.60 (ddd, J = 10.9, 8.0, 7.0 Hz, 143.96, 142.18, 1156 found, 1H), 4.10 (s, 2H), 3.90 (s, 3H), 135.58 (d, J = 3.2 Hz), 658.2905 3.59 (q, J = 7.0 Hz, 2H), 130.06 (d, J = 7.7 Hz), 2.81-2.69 (m, 1H), 2.66 (dd, J = 13.8, 115.22 (d, J = 21.2 Hz), 3.8 Hz, 1H), 109.72, 89.51, 75.54, 2.43-2.28 (m, 2H), 2.01-1.45 (m, 11H), 73.17, 67.78, 67.17, 1.34-1.17 (m, 2H), 1.29 (d, J = 5.7 Hz, 56.22, 51.73, 44.14, 3H), 1.23 (t, J = 7.0 Hz, 44.01, 35.93, 33.43, 3H), 1.05-0.92 (m, 1H) 30.06, 30.04, 26.83, 25.72, 25.69, 18.72, 17.55, 15.00 ¹⁹F NMR (CDCl₃) δ −117.11 F171 118-120 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 176.44, 172.68, 2976, ([M]⁺) 1H), 7.13-7.02 (m, 2H), 170.05, 162.90, 2939, calcd for 7.02-6.90 (m, 3H), 5.81 (s, 161.35 (d, J = 244.0 Hz), 1734, C₃₂H₄₁FN₂O₁₀, 2H), 5.12-4.96 (m, 2H), 160.17, 145.75, 1677, 632.2745; 4.68-4.54 (m, 1H), 4.10 (s, 2H), 143.94, 142.17, 1507, found, 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 135.53 (d, J = 3.2 Hz), 1153 632.2746 2H), 2.65 (dd, J = 14.0, 130.05 (d, J = 7.8 Hz), 3.6 Hz, 1H), 2.58 (hept, J = 7.0 Hz, 115.22 (d, J = 21.1 Hz), 1H), 2.45-2.26 (m, 2H), 109.74, 89.48, 75.48, 2.00-1.85 (m, 1H), 73.10, 67.77, 67.16, 1.77-1.43 (m, 3H), 1.29 (d, J = 5.6 Hz, 56.22, 51.73, 44.11, 3H), 1.29-1.15 (m, 10H), 35.85, 34.21, 33.41, 1.05-0.91 (m, 1H) 26.76, 19.07, 18.98, 18.72, 17.49, 15.00 ¹⁹F NMR (CDCl₃) δ −117.07 F172 — — ESIMS ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ m/z 601.7 1H), 8.26 (d, J = 5.3 Hz, 172.72, 170.04, ([M + H]⁺) 1H), 7.33-7.23 (m, 3H), 162.89, 160.15, 7.23-7.13 (m, 3H), 6.93 (d, J = 5.4 Hz, 145.78, 143.87, 1H), 5.81 (s, 2H), 142.31, 140.85, 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 128.86, 128.34, 4.57 (dt, J = 10.9, 7.5 Hz, 1H), 125.87, 109.67, 89.55, 4.09 (s, 2H), 3.90 (s, 3H), 83.71, 80.65, 75.30, 3.65-3.51 (m, 3H), 3.34 (dd, J = 8.4, 67.79, 67.18, 56.21, 6.5 Hz, 1H), 51.77, 46.19, 36.73, 3.20-3.03 (m, 2H), 2.42-2.21 (m, 2H), 33.70, 29.70, 29.28, 1.98-1.76 (m, 2H), 26.56, 19.55, 19.50, 1.63-1.53 (m, 2H), 1.50-1.40 (m, 18.84, 18.18, 15.01 overlapping, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.31-1.15 (m, 7H), 0.97 (dd, J = 6.7, 5.2 Hz, 6H), 0.92-0.80 (m, 2H) F173 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 599.6 1H), 8.26 (d, J = 5.4 Hz, 172.70, 170.04, ([M + H]⁺) 1H), 7.38-7.23 (m, 2H), 162.89, 160.15, 7.23-7.15 (m, 3H), 6.93 (d, J = 5.4 Hz, 145.79, 143.86, 1H), 5.81 (s, 2H), 142.30, 140.72, 4.93 (dq, J = 9.0, 6.4 Hz, 1H), 128.88, 128.35, 4.57 (dt, J = 10.9, 7.5 Hz, 1H), 125.90, 109.67, 89.53, 4.09 (s, 2H), 3.90 (s, 3H), 83.81, 78.75, 75.25, 3.61-3.52 (m, 3H), 3.45 (dd, J = 9.7, 67.79, 67.18, 56.21, 6.8 Hz, 1H), 51.75, 46.05, 36.89, 3.26-3.09 (m, 2H), 2.44-2.22 (m, 2H), 33.69, 29.70, 26.60, 1.89 (ddq, J = 12.0, 7.4, 3.7 Hz, 18.77, 18.11, 15.01, 1H), 1.57 (ddd, J = 12.3, 11.17, 3.16, 3.01 6.4, 2.5 Hz, 2H), 1.51-1.40 (m, overlapping, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.32-1.18 (m, 3H), 1.17-1.10 (m, 1H), 0.96-0.78 (m, 2H), 0.64-0.51 (m, 2H), 0.26 (dd, J = 5.8, 3.7 Hz, 2H) F174 — — ESIMS ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 587.5 1H), 8.26 (d, J = 5.3 Hz, 172.72, 170.04, ([M + H]⁺) 1H), 7.35-7.23 (m, 2H), 162.89, 160.15, 7.23-7.13 (m, 3H), 6.93 (d, J = 5.4 Hz, 145.79, 143.87, 1H), 5.81 (s, 2H), 142.31, 140.80, 4.91 (dq, J = 9.2, 6.4 Hz, 1H), 128.87, 128.34, 4.57 (ddd, J = 10.9, 8.2, 7.0 Hz, 125.88, 109.68, 89.54, 1H), 4.09 (s, 2H), 3.89 (s, 84.00, 75.60, 75.26, 3H), 3.74 (dt, J = 8.7, 6.6 Hz, 67.79, 67.18, 56.21, 1H), 3.66-3.47 (m, 3H), 51.76, 46.06, 36.83, 3.18 (t, J = 9.1 Hz, 1H), 3.11 (dd, J = 13.3, 33.70, 26.60, 23.59, 3.4 Hz, 1H), 18.81, 18.11, 15.01, 2.42-2.23 (m, 2H), 1.85 (ddt, J = 12.1, 10.74 8.2, 3.7 Hz, 1H), 1.70-1.53 (m, 4H), 1.51-1.40 (m, overlapping, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.36-1.11 (m, 4H), 0.98 (t, J = 7.4 Hz, 3H), 0.91-0.81 (m, 1H) F175 — — ESIMS ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 607.6 1H), 8.27 (d, J = 5.3 Hz, 172.83, 170.05, ([M + H]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.88, 160.15, 1H), 5.82 (s, 2H), 4.87 (dq, J = 9.2, 145.79, 143.87, 6.3 Hz, 1H), 142.35, 109.67, 89.54, 4.61-4.48 (m, 1H), 4.10 (s, 2H), 3.90 (s, 84.31, 80.37, 75.49, 3H), 3.59 (q, J = 7.0 Hz, 2H), 67.78, 67.17, 56.21, 3.46 (dd, J = 8.4, 6.1 Hz, 1H), 51.85, 40.03, 38.13, 3.24 (dd, J = 8.4, 6.7 Hz, 1H), 35.08, 34.58, 33.73, 2.98 (t, J = 8.8 Hz, 1H), 32.26, 29.20, 27.45, 2.34 (dt, J = 13.2, 6.7 Hz, 1H), 26.69, 26.51, 26.20, 1.83 (dp, J = 13.2, 6.6 Hz, 2H), 19.58, 19.46, 18.85, 1.77-1.50 (m, 9H), 1.41 (d, J = 6.4 Hz, 18.16, 15.00 3H), 1.39-1.11 (m, 10H), 1.02-0.92 (m, 8H), 0.76 (tt, J = 11.6, 6.3 Hz, 1H) F176 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.80, 170.06, ([M]⁺) 1H), 7.35-7.23 (m, 2H), 162.92, 160.18, calcd for 7.02-6.88 (m, 4H), 5.82 (s, 159.77, 145.80, C₃₃H₄₄N₂O₉, 2H), 5.07 (dq, J = 9.2, 6.4 Hz, 143.93, 142.30, 612.3047; 1H), 4.61 (ddd, J = 10.8, 8.1, 129.58, 120.94, found, 7.0 Hz, 1H), 4.18 (t, J = 8.7 Hz, 115.56, 109.71, 89.55, 612.3053 1H), 4.10 (s, 2H), 3.90 (s, 81.66, 74.90, 67.80, 3H), 3.59 (q, J = 7.0 Hz, 2H), 67.19, 56.23, 51.93, 2.48-2.34 (m, 1H), 42.03, 37.27, 36.85, 1.93-1.33 (m, 14H), 1.30 (d, J = 6.5 Hz, 33.70, 33.66, 31.77, 3H), 1.27-1.19 (m, 3H), 27.62, 25.05, 19.11, 1.20-1.06 (m, 1H), 18.40, 15.02 1.07-0.90 (m, 2H) F177 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.71, 170.04, ([M]⁺) 1H), 7.09 (d, J = 8.6 Hz, 162.89, 160.16, calcd for 2H), 6.93 (d, J = 5.4 Hz, 1H), 157.83, 145.79, C₃₃H₄₄N₂O₁₀, 6.83 (d, J = 8.6 Hz, 2H), 143.88, 142.32, 628.2996; 5.81 (s, 2H), 4.92 (dq, J = 9.2, 6.4 Hz, 132.68, 129.74, found, 1H), 4.56 (ddd, J = 10.9, 113.78, 109.67, 89.55, 628.3010 8.2, 7.0 Hz, 1H), 4.09 (s, 2H), 83.82, 78.76, 75.27, 3.90 (s, 3H), 3.79 (s, 3H), 67.80, 67.18, 56.21, 3.59 (q, J = 7.0 Hz, 3H), 3.45 (dd, J = 9.7, 55.24, 51.76, 46.18, 6.8 Hz, 1H), 3.16 (t, J = 9.1 Hz, 35.93, 33.72, 26.56, 1H), 3.08 (dd, J = 13.2, 18.77, 18.11, 15.02, 3.3 Hz, 1H), 11.18, 3.16, 3.01 2.37-2.22 (m, 2H), 1.83 (ddt, J = 12.1, 8.4, 3.8 Hz, 1H), 1.67-1.51 (m, 3H), 1.46 (d, J = 6.4 Hz, 3H), 1.26-1.18 (m, 1H), 1.23 (t, J = 7.0 Hz, 3H), 1.17-1.05 (m, 1H), 0.87 (d, J = 15.1 Hz, 1H), 0.62-0.54 (m, 2H), 0.31-0.19 (m, 2H) F178 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.82, 170.05, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.89, 160.16, calcd for 1H), 5.82 (d, J = 0.8 Hz, 2H), 145.80, 143.89, C₃₁H₄₆N₂O₉, 4.89 (dq, J = 9.3, 6.4 Hz, 1H), 142.36, 109.66, 89.58, 590.3203; 4.64-4.43 (m, 1H), 4.10 (s, 84.35, 78.54, 75.39, found, 3H), 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 67.80, 67.19, 56.21, 590.3225 2H), 3.50 (dd, J = 9.6, 51.86, 42.33, 37.26, 7.0 Hz, 1H), 3.36 (dd, J = 9.6, 36.90, 33.96, 33.76, 6.8 Hz, 1H), 3.00 (t, J = 8.9 Hz, 31.84, 27.54, 25.10, 1H), 2.34 (dt, J = 13.3, 6.8 Hz, 25.07, 18.97, 18.10, 1H), 1.93-1.45 (m, 12H), 15.01, 11.14, 3.14, 1.42 (d, J = 6.5 Hz, 3H), 2.94 1.37-1.27 (m, 1H), 1.23 (t, J = 7.0 Hz, 3H), 1.15-0.90 (m, 4H), 0.62-0.50 (m, 2H), 0.21 (dt, J = 5.9, 4.5 Hz, 2H) F179 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.26 (d, J = 5.3 Hz, 172.73, 170.04, ([M]⁺) 1H), 7.08 (d, J = 8.6 Hz, 162.88, 160.15, calcd for 2H), 6.94 (d, J = 5.4 Hz, 1H), 157.80, 145.79, C₃₃H₄₆N₂O₁₀, 6.83 (d, J = 8.6 Hz, 2H), 143.87, 142.31, 630.3152; 5.81 (s, 2H), 4.91 (dq, J = 9.2, 6.4 Hz, 132.81, 129.71, found, 1H), 4.56 (ddd, J = 10.9, 113.76, 109.68, 89.54, 630.3164 8.1, 7.0 Hz, 1H), 4.09 (s, 2H), 83.71, 80.63, 75.31, 3.89 (s, 3H), 3.78 (s, 3H), 67.79, 67.18, 56.22, 3.66-3.50 (m, 3H), 3.34 (dd, J = 8.4, 55.23, 51.77, 46.32, 6.5 Hz, 1H), 3.14 (t, J = 9.0 Hz, 35.78, 33.71, 29.27, 1H), 3.04 (dd, J = 13.4, 26.53, 19.55, 19.50, 3.2 Hz, 1H), 18.84, 18.18, 15.02 2.35-2.23 (m, 2H), 1.97-1.73 (m, 2H), 1.64-1.51 (m, 2H), 1.45 (d, J = 6.4 Hz, 3H), 1.30-1.13 (m, 5H), 0.97 (dd, J = 6.7, 5.2 Hz, 6H), 0.94-0.79 (m, 1H) F180 50-55 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J = 8.1 Hz, m/z 613 1H), 8.25 (s, 1H), ([M + H]⁺) 7.12-7.03 (m, 4H), 6.93 (d, J = 5.4 Hz, ¹³C NMR (CDCl₃) δ 1H), 5.80 (s, 2H), 172.65, 169.98, 4.91 (dq, J = 9.2, 6.4 Hz, 1H), 162.83, 160.09, 4.55 (ddd, J = 10.9, 8.2, 7.0 Hz, 145.74, 143.80, 1H), 4.08 (s, 2H), 3.88 (s, 142.23, 137.49, 3H), 3.58 (q, J = 7.0 Hz, 2H), 135.29, 128.98, 3.58 (dd, J = 9.7, 7.0 Hz, 1H), 128.68, 109.63, 89.47, 3.44 (dd, J = 9.7, 6.9 Hz, 1H), 83.74, 78.69, 75.20, 3.16 (t, J = 9.1 Hz, 1H), 67.73, 67.11, 56.16, 3.09 (dd, J = 13.2, 3.3 Hz, 1H), 51.69, 46.01, 36.33, 2.39-2.21 (m, 5H), 33.64, 26.49, 20.96, 1.93-1.80 (m, 1H), 1.63-1.51 (m, 18.69, 18.05, 14.96, 2H), 1.51-1.40 (m, 4H), 11.12, 3.10, 2.95 1.30-1.07 (m, 5H), 0.90-0.80 (m, 1H), 0.61-0.54 (m, 2H), 0.28-0.20 (m, 2H) F181 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.76, 170.06, ([M + Na]⁺) 1H), 6.94 (d, J = 5.5 Hz, 162.90, 160.18, calcd for 1H), 5.82 (s, 2H), 4.90 (dq, J = 9.1, 145.80, 143.91, C₂₇H₄₁FN₂O₉Na, 6.4 Hz, 1H), 142.30, 109.69, 89.57, 579.2688; 4.64-4.51 (m, 2H), 4.51-4.39 (m, 1H), 83.86, 83.81, 82.17, found 4.10 (s, 2H), 3.90 (s, 3H), 80.23, 75.26, 67.80, 579.2694 3.59 (q, J = 7.0 Hz, 2H), 3.45 (dd, J = 8.4, 67.19, 56.22, 51.86, 6.6 Hz, 1H), 3.26 (dd, J = 8.4, 39.77, 39.73, 33.56, 6.4 Hz, 1H), 31.62, 31.42, 29.17, 3.14-3.02 (m, 1H), 2.35 (dt, J = 12.9, 6.7 Hz, 28.72, 19.46, 19.42, 1H), 2.15-1.96 (m, 1H), 19.19, 18.14, 15.02 1.83 (dq, J = 13.3, 6.7 Hz, 1H), 1.78-1.60 (m, 4H), 1.56 (s, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.39-1.29 (m, 1H), 1.23 (t, J = 7.0 Hz, 3H), 1.10 (dd, J = 14.0, 6.8 Hz, 1H), 0.96-0.89 (m, 6H) F182 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.74, 170.07, ([M + H]⁺) 1H), 7.33-7.27 (m, 2H), 162.93, 160.18, calcd for 7.26-7.21 (m, 2H), 159.35, 158.78, C₃₅H₄₃N₂O₁₀, 7.02-6.88 (m, 5H), 6.88-6.78 (m, 145.80, 143.96, 651.2912; 2H), 5.82 (s, 2H), 142.24, 129.69, found, 5.18-5.06 (m, 1H), 4.62 (dt, J = 10.9, 7.0 Hz, 129.39, 121.18, 651.2930 1H), 4.29 (t, J = 8.7 Hz, 120.61, 115.42, 1H), 4.10 (s, 2H), 3.96 (t, J = 6.1 Hz, 114.46, 109.72, 89.56, 2H), 3.91 (s, 3H), 81.16, 74.79, 67.81, 3.59 (q, J = 7.0 Hz, 2H), 2.40 (dt, J = 12.7, 67.19, 66.05, 56.23, 6.7 Hz, 1H), 51.90, 40.21, 33.58, 2.15-2.02 (m, 2H), 1.99-1.83 (m, 30.54, 28.47, 19.32, 1H), 1.83-1.62 (m, 3H), 18.34, 15.02 1.40 (q, J = 12.3, 11.7 Hz, 1H), 1.32 (d, J = 6.5 Hz, 3H), 1.23 (m, 4H) F183 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.74, 170.07, ([M + H]⁺) 1H), 7.32-7.27 (m, 2H), 162.92, 160.18, calcd for 6.99-6.90 (m, 4H), 5.82 (s, 159.46, 145.80, C₃₀H₄₁N₂O₁₀, 2H), 5.08 (dq, J = 9.1, 6.5 Hz, 143.95, 142.27, 589.2756; 1H), 4.61 (dt, J = 10.8, 7.0 Hz, 129.62, 121.06, found, 1H), 4.24 (t, J = 8.8 Hz, 1H), 115.38, 109.71, 89.56, 589.2763 4.10 (s, 2H), 3.91 (s, 3H), 81.12, 74.84, 70.80, 3.59 (q, J = 7.0 Hz, 2H), 3.38 (t, J = 6.8 Hz, 67.80, 67.19, 58.44, 2H), 3.26 (s, 3H), 56.23, 51.89, 40.13, 2.40 (dt, J = 12.3, 6.7 Hz, 1H), 33.63, 30.56, 28.15, 1.99-1.78 (m, 3H), 1.78-1.61 (m, 19.18, 18.35, 15.02 2H), 1.48 (ddd, J = 13.6, 9.9, 6.7 Hz, 1H), 1.39 (q, J = 11.0 Hz, 1H), 1.30 (d, J = 6.5 Hz, 3H), 1.23 (t, J = 7.0 Hz, 3H), 1.17 (d, J = 7.5 Hz, 1H) F184 — — ESIMS ¹H NMR (CDCl₃) δ 8.52 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ m/z 527.3 1H), 8.34 (d, J = 5.4 Hz, 172.65, 168.71, ([M + H]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.20, 159.41, 1H), 4.89 (dq, J = 9.0, 6.4 Hz, 146.89, 141.38, 1H), 4.55 (tt, J = 10.9, 4.4 Hz, 137.00, 109.84, 83.85, 2H), 4.48 (s, 2H), 4.44 (ddd, J = 7.7, 83.79, 82.15, 80.20, 5.9, 2.6 Hz, 1H), 75.24, 67.86, 67.36, 3.90 (d, J = 1.8 Hz, 3H), 3.73 (q, J = 7.0 Hz, 56.30, 51.57, 39.75, 2H), 3.44 (dd, J = 8.4, 33.73, 31.61, 31.42, 6.6 Hz, 1H), 3.26 (dd, J = 8.4, 29.17, 28.70, 19.45, 6.4 Hz, 1H), 19.41, 19.14, 18.11, 3.10-3.02 (m, 1H), 2.32 (dt, J = 12.9, 6.7 Hz, 15.08 1H), 2.13-1.97 (m, 1H), 1.84 (dp, J = 13.2, 6.6 Hz, 1H), 1.78-1.64 (m, 3H), 1.60-1.45 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.37-1.31 (m, 1H), 1.29 (t, J = 7.0 Hz, 3H), 1.08 (dd, J = 12.1, 5.0 Hz, 1H), 0.92 (d, J = 6.6 Hz, 6H) F185 — — ESIMS ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ m/z 621.3 1H), 8.35 (d, J = 5.4 Hz, 172.64, 168.72, ([M + H]⁺) 1H), 7.35-7.27 (m, 2H), 162.23, 159.43, 7.25-7.20 (m, 2H), 7.01 (d, J = 5.5 Hz, 159.35, 158.78, 1H), 6.99-6.88 (m, 146.89, 141.35, 4H), 6.82 (dd, J = 8.7, 1.0 Hz, 137.04, 129.69, 2H), 5.11 (dq, J = 9.1, 6.4 Hz, 129.39, 121.19, 1H), 4.61 (ddd, J = 10.9, 8.2, 120.61, 115.42, 7.0 Hz, 1H), 4.48 (s, 2H), 114.46, 109.87, 81.18, 4.28 (t, J = 8.7 Hz, 1H), 3.95 (t, J = 6.0 Hz, 74.77, 67.87, 67.37, 2H), 3.90 (s, 3H), 66.05, 56.31, 51.63, 3.73 (q, J = 7.0 Hz, 2H), 2.37 (dt, J = 12.9, 40.21, 33.75, 30.54, 6.6 Hz, 1H), 2.07 (td, J = 9.0, 28.48, 19.29, 18.32, 7.1, 3.6 Hz, 2H), 15.08 1.96-1.82 (m, 1H), 1.82-1.62 (m, 3H), 1.44-1.34 (m, 1H), 1.33-1.26 (m, 6H), 1.26-1.18 (m, 1H) F186 — — ESIMS ¹H NMR (CDCl₃) δ 8.53 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 559.3 1H), 8.35 (d, J = 5.4 Hz, 172.64, 168.72, ([M + H]⁺) 1H), 7.33-7.27 (m, 2H), 162.21, 159.46, 7.01 (d, J = 5.5 Hz, 1H), 146.88, 141.37, 6.94 (dd, J = 8.0, 3.2 Hz, 3H), 129.62, 121.06, 5.15-5.00 (m, 1H), 4.60 (dt, J = 10.8, 115.39, 109.86, 81.14, 7.1 Hz, 1H), 4.48 (s, 2H), 74.82, 70.81, 67.86, 4.23 (t, J = 8.8 Hz, 1H), 67.36, 58.44, 56.30, 3.90 (s, 3H), 3.73 (q, J = 7.0 Hz, 51.61, 40.12, 33.79, 2H), 3.37 (t, J = 6.6 Hz, 2H), 30.57, 28.17, 19.16, 3.26 (s, 3H), 2.37 (dt, J = 13.0, 18.33, 15.07 6.7 Hz, 1H), 1.98-1.76 (m, 3H), 1.76-1.61 (m, 2H), 1.56-1.42 (m, 1H), 1.42-1.32 (m, 1H), 1.29 (dt, J = 7.0, 3.8 Hz, 6H), 1.18 (dd, J = 15.2, 7.5 Hz, 1H) F187 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.76, 170.02, [M + Na]⁺ 1H), 6.96 (d, J = 5.5 Hz, 162.86, 160.13, calcd for 1H), 5.82 (s, 2H), 4.88 (dq, J = 9.0, 145.79, 143.82, C₂₈H₄₄O₁₀N₂Na, 6.4 Hz, 1H), 4.56 (dt, J = 10.8, 142.27, 109.70, 89.47, 591.2888; 7.1 Hz, 1H), 4.10 (s, 2H), 84.00, 80.30, 75.35, found, 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 71.21, 67.75, 67.13, 591.2914 2H), 3.42 (q, J = 7.8, 7.2 Hz, 58.46, 56.21, 51.83, 3H), 3.32 (s, 3H), 40.21, 33.57, 30.37, 3.29 (dd, J = 8.1, 6.1 Hz, 1H), 29.13, 28.33, 19.48, 3.05 (t, J = 8.8 Hz, 1H), 2.34 (dt, J = 13.2, 19.40, 19.08, 18.12, 6.5 Hz, 1H), 1.97 (dtd, 14.99 J = 10.8, 7.5, 3.2 Hz, 1H), 1.85 (dp, J = 13.2, 6.6 Hz, 1H), 1.67 (ddt, J = 27.8, 14.0, 6.7 Hz, 3H), 1.59-1.44 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.33 (q, J = 11.3 Hz, 1H), 1.23 (t, J = 7.0 Hz, 3H), 1.10-1.00 (m, 1H), 0.92 (dd, J = 6.7, 2.5 Hz, 6H) F188 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.52 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 172.70, 168.72, [M + Na]⁺ 1H), 7.00 (d, J = 5.5 Hz, 162.18, 159.41, calcd for 1H), 4.94-4.82 (m, 1H), 146.88, 141.42, C₂₇H₄₂O₉N₂Na, 4.54 (ddd, J = 10.8, 8.2, 7.0 Hz, 137.00, 109.82, 84.04, 561.2783; 1H), 4.48 (s, 2H), 3.90 (s, 3H), 80.33, 75.38, 71.28, found, 3.73 (q, J = 7.0 Hz, 2H), 67.86, 67.36, 58.51, 561.2802 3.41 (q, J = 7.4, 6.6 Hz, 3H), 56.30, 51.58, 40.25, 3.32 (s, 3H), 3.32-3.26 (m, 1H), 33.82, 30.42, 29.17, 3.03 (t, J = 8.8 Hz, 1H), 28.36, 19.51, 19.43, 2.31 (dt, J = 13.2, 6.5 Hz, 1H), 19.07, 18.13, 15.08 1.96 (dtd, J = 10.6, 7.4, 3.1 Hz, 1H), 1.83 (dq, J = 13.3, 6.6 Hz, 1H), 1.75-1.63 (m, 2H), 1.62 (s, 1H), 1.56-1.44 (m, 2H), 1.40 (d, J = 6.4 Hz, 3H), 1.29 (m, 4H), 1.03 (dd, J = 13.3, 5.9 Hz, 1H), 0.91 (dd, J = 6.7, 2.7 Hz, 6H) F189 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.79, 170.07, [M + H]⁺ 1H), 7.30 (d, J = 7.7 Hz, 162.92, 160.18, calcd for 2H), 6.94 (dd, J = 7.1, 4.6 Hz, 159.68, 145.80, C₂₉H₃₉O₉N₉, 4H), 5.83 (s, 2H), 143.95, 142.29, 559.2650; 5.16-5.01 (m, 1H), 4.61 (dt, J = 10.8, 7.4 Hz, 129.60, 120.95, found, 1H), 4.22 (t, J = 8.8 Hz, 115.40, 109.70, 99.98, 559.2654 1H), 4.10 (s, 2H), 3.91 (s, 3H), 89.57, 81.44, 74.86, 3.59 (q, J = 7.0 Hz, 2H), 67.81, 67.19, 56.23, 2.40 (dt, J = 12.5, 6.4 Hz, 1H), 51.89, 44.98, 33.68, 1.95-1.78 (m, 1H), 1.77-1.59 (m 27.05, 23.53, 18.85, 4H), 1.38 (q, J = 12.7, 11.9 Hz, 18.38, 15.02, 11.88, 1H), 1.30 (d, J = 6.4 Hz, 0.00 3H), 1.27-1.19 (m, 4H), 1.17 (s, 1H), 0.88 (t, J = 7.2 Hz, 3H) F190 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 669 1H), 8.25 (d, J = 5.4 Hz, 172.62, 169.97, [M + H]⁺ 1H), 7.09 (d, J = 7.9 Hz, 162.83, 160.09, 2H), 7.03 (d, J = 8.0 Hz, 2H), 145.73, 143.81, 6.93 (d, J = 5.4 Hz, 1H), 142.18, 137.20, 5.80 (s, 2H), 4.89 (dq, J = 9.1, 6.4 Hz, 135.41, 129.02, 1H), 4.55 (dt, J = 10.9, 7.4 Hz, 128.58, 1H), 4.08 (s, 2H), 3.88 (s, 131.42-122.86 (m), 109.65, 3H), 3.80 (dt, J = 8.9, 6.1 Hz, 89.44, 84.20, 74.83, 1H), 3.64-3.54 (m, 3H), 71.60, 67.71, 67.10, 3.17 (t, J = 9.0 Hz, 1H), 2.96 (dd, J = 13.3, 56.15, 51.69, 45.80, 3.4 Hz, 1H), 36.42, 33.56, 30.73 (q, 2.40-2.13 (m, 7H), 1.92-1.76 (m, J = 29.0 Hz), 26.62, 3H), 1.65-1.37 (m, 6H), 23.01 (q, J = 3.1 Hz), 1.30-1.14 (m, 4H), 0.93-0.80 (m, 20.93, 18.75, 18.05, 1H) 14.94 ¹⁹F NMR (CDCl₃) δ −66.35 F191 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.14 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.07 (d, J = 5.4 Hz, 172.74, 170.02, [M + H]⁺ 1H), 6.75 (d, J = 5.5 Hz, 162.87, 160.13, calcd for 1H), 5.61 (s, 2H), 4.69 (dq, J = 9.0, 145.78, 143.84, C₃₁H₄₇O₁₀N₂, 6.4 Hz, 1H), 4.35 (dt, J = 10.7, 142.29, 109.69, 89.49, 607.3225; 7.2 Hz, 1H), 3.89 (s, 2H), 84.00, 78.33, 75.41, found, 3.70 (s, 3H), 3.39 (q, J = 7.0 Hz, 75.30, 69.06, 67.76, 607.3236 2H), 3.34-3.15 (m, 4H), 67.14, 56.21, 51.80, 3.05 (dq, J = 6.5, 3.3 Hz, 2H), 40.47, 33.62, 30.66, 2.88 (t, J = 8.9 Hz, 1H), 28.20, 19.02, 18.07, 2.14 (dt, J = 13.2, 6.5 Hz, 1H), 14.99, 11.08, 10.64, 1.90-1.72 (m, 1H), 1.48 (dtd, J = 21.5 3.15, 2.99, 2.92, 2.87 11.5, 10.3, 6.2 Hz, 3H), 1.40-1.26 (m, 2H), 1.22 (d, J = 6.4 Hz, 3H), 1.13 (q, J = 11.4 Hz, 1H), 1.02 (t, J = 7.0 Hz, 3H), 0.85 (dddd, J = 14.8, 6.8, 5.0, 3.5 Hz, 3H), 0.33 (tdd, J = 10.0, 4.9, 3.7 Hz, 4H), 0.00 (dtd, J = 10.2, 5.3, 4.7, 2.9 Hz, 4H) F192 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.43 (d, J = 7.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (dd, J = 5.3, 173.60, 170.02, [M + H]⁺ 3.3 Hz, 1H), 6.96 (dd, J = 5.4, 162.79, 160.14, calcd for 1.7 Hz, 1H), 5.82 (d, J = 2.9 Hz, 145.80, 143.84, C₂₃H₃₃O₉N₂, 2H), 4.99 (ddt, J = 12.6, 142.28, 109.71, 89.47, 481.2181; 9.2, 4.7 Hz, 1H), 86.82, 73.26, 67.74, found, 4.61-4.41 (m, 1H), 4.10 (d, J = 2.8 Hz, 67.68, 67.13, 56.21, 481.2183 2H), 3.90 (d, J = 2.7 Hz, 53.27, 39.67, 36.07, 3H), 3.80 (td, J = 7.5, 6.5, 3.2 Hz, 35.73, 32.37, 21.77, 1H), 3.69 (dq, J = 8.8, 5.5, 18.36, 14.98 4.7 Hz, 1H), 3.59 (qd, J = 7.0, 2.7 Hz, 2H), 3.42 (tt, J = 6.6, 2.9 Hz, 1H), 2.47-2.31 (m, 1H), 2.15-1.82 (m, 3H), 1.75 (t, J = 14.0 Hz, 1H), 1.63 (t, J = 13.1 Hz, 1H), 1.57-1.46 (m, 2H), 1.41 (dt, J = 9.7, 4.8 Hz, 4H), 1.23 (td, J = 7.0, 3.0 Hz, 3H) F193 70-75 — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 675 1H), 8.22 (d, J = 5.4 Hz, 172.50, 169.95, ([M + H]⁺) 1H), 7.59 (dd, J = 1.7, 0.8 Hz, 162.79, 161.38 (dd, J = 246.4, 1H), 7.15 (dd, J = 3.5, 0.8 Hz, 11.5 Hz), 1H), 7.03 (td, J = 8.5, 6.4 Hz, 160.89 (dd, J = 247.5, 1H), 6.92 (d, J = 5.4 Hz, 11.6 Hz), 160.05, 1H), 6.73-6.63 (m, 2H), 158.08, 146.84, 6.50 (dd, J = 3.5, 1.7 Hz, 1H), 145.65, 143.82, 5.78 (s, 2H), 5.19 (t, J = 9.2 Hz, 143.80, 142.02, 1H), 5.09 (dq, J = 9.5, 6.2 Hz 131.50 (dd, J = 9.4 6.5 Hz) 1H), 4.59 (dt, J = 10.9, 7.4 Hz, 122.36 (dd, J = 15.7, 1H), 4.06 (s, 2H), 3.86 (s, 3H), 111.89, 110.82 (dd, J = 21.0, 3.56 (q, J = 7.0 Hz, 2H), 3.6 Hz), 2.70 (dd, J = 13.9, 4.5 Hz, 1H), 109.65, 103.58 (t, J = 25.7 Hz), 2.50 (dd, J = 13.9, 10.3 Hz, 56.11, 51.59, 42.51, 1H), 2.39-2.29 (m, 1H), 33.28, 29.98, 27.26, 2.18-2.07 (m, 1H), 1.74-1.51 (m, 18.66, 17.40, 14.88 3H), 1.30 (d, J = 6.3 Hz, 3H), ¹⁹F NMR (CDCl₃) δ 1.28-1.21 (m, 1H), 1.19 (t, J = 7.0 Hz, −112.99 (d, J = 6.8 Hz), 3H), 1.11-0.99 (m, −113.49 (d, J = 6.9 Hz) 1H) F194 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.51 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.72, 169.40, ([M]⁺) 1H), 6.99 (d, J = 5.5 Hz, 162.31, 159.40, calcd for 1H), 4.88 (dq, J = 9.2, 6.4 Hz, 146.75, 141.50, C₃₀H₄₄N₂O₈, 1H), 4.54 (ddd, J = 10.8, 8.4, 137.29, 109.75, 84.34, 560.3098; 7.0 Hz, 1H), 3.89 (s, 3H), 78.49, 75.34, 67.58, found, 3.81 (t, J = 6.6 Hz, 2H), 3.49 (dd, J = 9.6, 58.77, 56.30, 51.57, 560.3112 7.0 Hz, 1H), 3.41 (s, 42.30, 37.25, 36.89, 3H), 3.39-3.28 (m, 2H), 34.62, 33.95, 33.92, 3.05-2.93 (m, 3H), 2.31 (dt, J = 13.4, 31.83, 27.54, 25.09, 6.8 Hz, 1H), 25.06, 18.93, 18.06, 1.91-1.65 (m, 4H), 1.65-1.43 (m, 8H), 11.13, 3.12, 2.93 1.40 (d, J = 6.5 Hz, 3H), 1.37-1.23 (m, 1H), 1.15-0.91 (m, 4H), 0.61-0.51 (m, 2H), 0.21 (dt, J = 5.8, 4.6 Hz, 2H) F195 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.47 (d, J = 7.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.31 (d, J = 5.4 Hz, 172.61, 169.39, ([M]⁺) 1H), 7.09 (d, J = 8.6 Hz, 162.32, 159.40, calcd for 2H), 6.98 (d, J = 5.5 Hz, 1H), 157.82, 146.76, C₃₂H₄₂N₂O₉, 6.83 (d, J = 8.6 Hz, 2H), 141.45, 137.29, 598.2890; 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 132.66, 129.73, found, 4.55 (ddd, J = 10.9, 8.4, 7.0 Hz, 113.77, 109.78, 83.79, 589.2914 1H), 3.88 (s, 3H), 3.81 (t, J = 6.6 Hz, 78.71, 75.22, 67.58, 2H), 3.78 (s, 3H), 58.78, 56.30, 55.22, 3.57 (dd, J = 9.7, 7.0 Hz, 1H), 51.47, 46.17, 35.92, 3.44 (dd, J = 9.7, 6.8 Hz, 1H), 34.62, 33.89, 26.55, 3.41 (s, 3H), 3.15 (t, J = 9.0 Hz, 18.73, 18.08, 11.18, 1H), 3.07 (dd, J = 13.4, 3.3 Hz, 3.16, 3.00 1H), 2.98 (t, J = 6.6 Hz, 2H), 2.35-2.20 (m, 2H), 1.87-1.77 (m, 1H), 1.61-1.47 (m, 2H), 1.48-1.37 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.22-1.05 (m, 2H), 0.90-0.79 (m, 1H), 0.63-0.49 (m, 2H), 0.29-0.14 (m, 2H) F196 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.50 (d, J = 7.7 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (d, J = 5.5 Hz, 172.75, 172.47, [M + H]⁺ 1H), 6.98 (d, J = 5.5 Hz, 162.31, 159.44, calcd for 1H), 5.01-4.75 (m, 1H), 146.62, 141.81, C₃₀H₄₃O₈N₂, 4.59 (dt, J = 10.6, 7.7 Hz, 1H), 137.40, 109.66, 99.97, 559.3014; 3.90 (s, 3H), 3.54-3.37 (m, 4H), 84.00, 78.38, 75.48, found, 3.25 (dq, J = 6.6, 3.3 Hz, 2H), 75.26, 69.12, 56.31, 559.3016 3.06 (t, J = 8.8 Hz, 1H), 51.46, 40.52, 33.93, 2.34 (dt, J = 13.4, 6.5 Hz, 1H), 30.65, 28.15, 18.94, 1.97 (tt, J = 8.2, 4.6 Hz, 2H), 18.06, 12.99, 11.09, 1.77-1.60 (m, 3H), 1.57-1.45 (m, 10.66, 9.31, 3.18, 3.02, 2H), 1.41 (d, J = 6.4 Hz, 3H), 2.95, 2.88 1.36-1.22 (m, 3H), 1.06 (ddt, J = 12.2, 8.6, 4.0 Hz, 5H), 0.60-0.47 (m, 4H), 0.30-0.14 (m, 4H) F197 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.47 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.64, 169.41, [M + H]⁺ 1H), 7.31-7.26 (m, 2H), 162.33, 159.41, calcd for 7.18 (tq, J = 7.4, 1.8 Hz, 3H), 146.76, 141.47, C₂₉H₃₉N₂O₈, 6.98 (d, J = 5.4 Hz, 1H), 140.75, 137.31, 543.2701; 4.90 (dq, J = 9.2, 6.4 Hz, 1H), 128.87, 128.34, found, 4.56 (ddd, J = 10.9, 8.4, 7.0 Hz, 125.89, 109.77, 84.20, 543.2705 1H), 3.89 (s, 3H), 75.19, 69.21, 67.59, 3.86-3.75 (m, 3H), 3.63 (dq, J = 8.9, 7.0 Hz, 58.79, 56.31, 51.49, 1H), 3.41 (s, 3H), 45.94, 36.91, 34.63, 3.22-3.13 (m, 1H), 3.09 (dd, J = 13.3, 33.89, 26.61, 18.75, 3.4 Hz, 1H), 2.98 (t, J = 6.6 Hz, 18.02, 15.73 2H), 2.35 (dd, J = 13.3, 11.6 Hz, 1H), 2.31-2.21 (m, 1H), 1.89-1.77 (m, 1H), 1.74-1.63 (m, 1H), 1.63-1.51 (m, 1H), 1.51-1.38 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.25 (t, J = 7.0 Hz, 3H), 1.22-1.12 (m, 1H), 0.92-0.79 (m, 1H) F198 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.47 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.64, 169.42, [M + H]⁺ 1H), 7.32-7.26 (m, 2H), 162.33, 159.41, calcd for 7.22-7.14 (m, 3H), 6.98 (d, J = 5.5 Hz, 146.75, 141.47, C₃₀H₄₁N₂O₈, 1H), 4.90 (dq, J = 9.2, 140.80, 137.31, 557.2857; 6.4 Hz, 1H), 4.56 (ddd, J = 10.9, 128.87, 128.34, found, 8.4, 7.0 Hz, 1H), 125.89, 109.77, 83.99, 557.2869 3.89 (s, 3H), 3.81 (t, J = 6.6 Hz, 75.58, 75.24, 67.59, 2H), 3.73 (dt, J = 8.8, 6.5 Hz, 58.79, 56.31, 51.49, 1H), 3.52 (dt, J = 8.7, 6.7 Hz, 46.06, 36.83, 34.62, 1H), 3.41 (s, 3H), 3.16 (t, J = 9.0 Hz, 33.89, 26.59, 23.60, 1H), 3.13-3.07 (m, 18.78, 18.09, 10.75 1H), 2.98 (t, J = 6.6 Hz, 2H), 2.35 (dd, J = 13.3, 11.7 Hz, 1H), 2.31-2.22 (m, 1H), 1.84 (ddq, J = 12.1, 7.6, 3.7 Hz, 1H), 1.73-1.51 (m, 4H), 1.51-1.36 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.29-1.07 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.92-0.82 (m, 1H) F199 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 456.3 7.28-7.09 (m, 2H), 6.96-6.75 (m, 172.32, 158.69, ([M + Na]⁺) 3H), 5.07 (d, J = 8.3 Hz, 1H), 153.90, 128.54, 5.02-4.88 (m, 1H), 119.93, 114.46, 80.59, 4.21-4.02 (m, 2H), 2.27-2.07 (m, 78.76, 73.72, 52.00, 1H), 1.81-1.29 (m, 7H), 42.14, 35.35, 33.09, 1.36 (s, 9H), 1.29-0.91 (m, 3H), 27.32, 27.21, 26.82, 1.21 (d, J = 6.4 Hz, 3H), 26.56, 22.02, 21.02, 0.82-0.73 (m, 1H), 0.72 (d, J = 6.6 Hz, 17.83, 17.39 3H), 0.71 (d, J = 6.7 Hz, 3H) F200 — — ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ m/z 436.4 1H), 4.90-4.75 (m, 173.40, 154.93, 84.31, ([M + Na]⁺) 1H), 4.21-4.07 (m, 1H), 80.43, 79.76, 75.36, 3.44 (dd, J = 8.4, 6.3 Hz, 1H), 52.97, 43.48, 36.53, 3.25 (dd, J = 8.4, 6.5 Hz, 1H), 34.21, 29.18, 28.33, 2.97 (t, J = 8.9 Hz, 1H), 28.10, 27.99, 27.55, 2.28-2.11 (m, 1H), 1.83 (hept, J = 6.6 Hz, 22.98, 22.27, 19.52, 1H), 1.75-1.41 (m, 8H), 19.46, 18.76, 18.19 1.44 (s, 9H), 1.39 (d, J = 6.4 Hz, 3H), 1.30-1.01 (m, 3H), 0.92 (d, J = 6.7 Hz, 3H), 0.91 (d, J = 6.7 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.87 (d, J = 6.6 Hz, 3H) F201 — — ESIMS ¹H NMR (CDCl₃) δ 5.08 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 434.4 1H), 4.86-4.68 (m, 173.35, 154.95, 84.37, ([M + Na]⁺) 1H), 4.14-4.01 (m, 1H), 79.69, 78.61, 75.28, 3.43 (dd, J = 9.6, 7.0 Hz, 1H), 52.97, 43.55, 36.43, 3.29 (dd, J = 9.7, 6.9 Hz, 1H), 34.16, 28.35, 28.05, 2.93 (t, J = 9.0 Hz, 1H), 27.38, 23.05, 22.22, 2.20-2.04 (m, 1H), 1.71-1.37 (m, 7H), 18.68, 18.14, 11.15, 1.37 (s, 9H), 1.34 (d, J = 6.5 Hz, 3.10, 3.03 3H), 1.25-0.92 (m, 5H), 0.82 (d, J = 6.6 Hz, 3H), 0.81 (d, J = 6.7 Hz, 3H), 0.53-0.43 (m, 2H), 0.20-0.09 (m, 2H) F202 — (Neat) ESIMS ¹H NMR (CDCl₃) δ — 2955, m/z 466.4 5.02-4.69 (m, 3H), 4.62-4.46 (m, 1750, ([M + Na]⁺) 0.5H), 4.25-4.10 (m, 0.5H), 1708, 3.70-3.55 (m, 1H), 1455, 3.49-3.40 (m, 1H), 3.40-3.28 (m, 1367, 3H), 3.07-2.93 (m, 1H), 1296, 2.18-1.98 (m, 1H), 1.81-1.42 (m, 1176, 17H), 1.40 (d, J = 6.4 Hz, 3H), 1083 1.35-1.01 (m, 4H), 0.93 (t, J = 7.5 Hz, 3H), 0.91-0.83 (m, 7H) F203 87-89 — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ m/z 534.4 5.02-4.69 (m, 3H), 4.62-4.45 (m, −66.42-−66.63 (m, 3F) ([M + Na]⁺) 0.5H), 4.27-4.09 (m, 0.5H), 3.82-3.65 (m, 1H), 3.61-3.47 (m, 1H), 3.42-3.26 (m, 3H), 3.09-2.93 (m, 1H), 2.31-1.95 (m, 3H), 1.92-1.42 (m, 17H), 1.39 (d, J = 6.4 Hz, 3H), 1.33-1.00 (m, 4H), 1.00-0.81 (m, 7H) F204 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2932, (m/z) 5.03-4.66 (m, 3H), 4.61-4.46 (m, 1765, ([M]⁺) 0.5H), 4.24-4.09 (m, 0.5H), 1707, calcd for 4.08-3.96 (m, 1H), 1454, C₂₆H₄₇NO₆, 3.42-3.27 (m, 3H), 3.17-3.04 (m, 1367, 469.3403; 1H), 2.23-1.99 (m, 1H), 1296, found, 1.86-0.99 (m, 30H), 1173, 469.3416 0.95-0.83 (m, 7H) 1083 F205 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2934, (m/z) 4.97-4.70 (m, 3H), 4.60-4.47 (m, 1747, ([M]⁺) 0.5H), 4.25-4.11 (m, 0.5H), 1705, calcd for 3.49 (s, 3H), 3.40-3.28 (m, 1454, C₂₂H₄₁NO₆, 3H), 2.97-2.86 (m, 1H), 1366, 415.2934; 2.17-2.01 (m, 1H), 1.79-1.42 (m, 1296, found, 16H), 1.42 (d, J = 6.4 Hz, 3H), 1170, 415.2943 1.31-1.07 (m, 3H), 1080 0.99-0.82 (m, 7H) F206 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2955, (m/z) 5.02-4.75 (m, 4H), 4.66-4.47 (m, 1735, ([M]⁺) 0.5H), 4.32-4.14 (m, 0.5H), 1705, calcd for 3.45-3.24 (m, 3H), 1454, C₂₇H₄₇NO₇, 2.85-2.65 (m, 1H), 2.22-1.36 (m, 1367, 497.3353; 25H), 1.35-0.94 (m, 7H), 1298, found, 0.93-0.76 (m, 6H) 1170 497.3368 F207 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ 2937, (m/z) 7.20-7.05 (m, 2H), 7.03-6.87 (m, 173.20, 170.99, 1748, ([M]⁺) 2H), 5.14 (d, J = 8.3 Hz, 1H), 161.24 (d, J = 243.7 Hz), 1714, calcd for 4.95-4.79 (m, 1H), 154.90, 136.32 (d, J = 3.2 Hz), 1509, C₂₅H₃₆FNO₅, 4.23-4.06 (m, 1H), 3.56 (dd, J = 9.7, 130.11 (d, J = 7.7 Hz), 1367, 449.2578; 7.0 Hz, 1H), 3.43 (dd, J = 9.7, 115.07 (d, J = 21.0 Hz), 1220, found, 6.8 Hz, 1H), 3.13-3.04 (m, 83.70, 79.67, 1160 449.2586 1H), 2.31 (dd, J = 13.4, 11.6 Hz, 78.68, 75.01, 60.30, 1H), 2.23-2.09 (m, 1H), 52.87, 46.08, 36.00, 1.86-1.72 (m, 1H), 33.98, 28.27, 26.62, 1.61-1.31 (m, 5H), 1.45 (d, J = 6.5 Hz, 20.95, 18.66, 18.07, 3H), 1.43 (s, 9H), 14.16, 11.15, 3.12, 1.19-0.99 (m, 1H), 0.89-0.75 (m, 2.97 1H), 0.62-0.52 (m, 2H), ¹⁹F NMR (CDCl₃) δ −117.40 0.29-0.20 (m, 2H) F208 75-77 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ 2936, (m/z) 7.36-7.26 (m, 2H), 7.12-6.86 (m, 173.26, 161.31 (d, J = 243.8 Hz), 1714, ([M]⁺) 7H), 5.17-4.96 (m, 2H), 159.56, 1509, calcd for 4.30 (t, J = 8.9 Hz, 1H), 154.89, 135.84 (d, J = 2.5 Hz), 1368, C₂₇H₃₄FNO₅, 4.26-4.16 (m, 1H), 2.95 (dd, J = 13.7, 3.5 Hz, 130.09 (d, J = 7.8 Hz), 1163 471.2421; 1H), 2.38-2.15 (m, 2H), 129.72, found, 2.09-1.95 (m, 1H), 121.26, 115.47, 471.2430 1.67-1.45 (m, 3H), 1.44 (s, 9H), 115.11 (d, J = 21.1 Hz), 1.33 (d, J = 6.5 Hz, 3H), 81.00, 79.93, 74.53, 1.18-0.90 (m, 2H) 52.94, 45.66, 36.09, 34.08, 28.33, 26.83, 18.83, 18.38 ¹⁹F NMR (CDCl₃) δ −117.34 F209 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.36, m/z 502.3 7.18-7.04 (m, 2H), 7.01-6.88 (m, −117.46 ([M + Na]⁺) 2H), 5.94 (ddt, J = 17.3, 10.7, 5.5 Hz, 1H), 5.39-5.27 (m, 1H), 5.19 (dd, J = 10.4, 1.7 Hz, 1H), 4.96-4.72 (m, 3H), 4.63-4.48 (m, 0.5H), 4.28 (dd, J = 12.4, 5.3 Hz, 1H), 4.25-4.16 (m, 0.5H), 4.13-4.03 (m, 1H), 3.39-3.14 (m, 3H), 3.05 (dd, J = 13.3, 3.4 Hz, 1H), 2.33 (dd, J = 13.4, 11.6 Hz, 1H), 2.19-1.97 (m, 1H), 1.88-1.72 (m, 1H), 1.73-1.33 (m, 17H), 0.93-0.77 (m, 1H) F210 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2936, (m/z) 7.18-7.05 (m, 2H), 7.03-6.88 (m, 1746, ([M]⁺) 2H), 4.98-4.68 (m, 3H), 1701, calcd for 4.63-4.49 (m, 0.5H), 1509, C₂₆H₄₀FNO₆, 4.27-4.15 (m, 0.5H), 3.80-3.63 (m, 1366, 481.2840; 1H), 3.57-3.43 (m, 1H), 1297, found, 3.39-3.23 (m, 2H), 3.20-3.08 (m, 1177 481.2842 1H), 3.05 (dt, J = 13.5, 3.5 Hz, 1H), 2.98-2.86 (m, 1H), 2.32 (t, J = 12.5 Hz, 1H), 2.17-2.00 (m, 1H), 1.94-1.32 (m, 19H), 0.97 (t, J = 7.4 Hz, 3H), 0.91-0.76 (m, 1H) F211 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2957, (m/z) 7.17-7.03 (m, 2H), 7.02-6.87 (m, 1748, ([M]⁺) 2H), 5.03-4.66 (m, 2H), 1705, calcd for 4.65-4.49 (m, 0.5H), 1509, C₂₇H₄₂FNO₆, 4.29-4.13 (m, 0.5H), 3.61-3.48 (m, 1367, 495.2996; 1H), 3.39-3.23 (m, 3H), 1296, found, 3.19-2.99 (m, 2H), 2.97-2.87 (m, 1175 495.2993 1H), 2.39-2.24 (m, 1H), 2.21-1.22 (m, 20H), 1.08-0.75 (m, 7H) F212 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.16, 2978, (m/z) 7.16-7.04 (m, 2H), 7.02-6.89 (m, −117.27, 2938, ([M]⁺) 2H), 5.86 (tt, J = 55.1, 4.0 Hz, −125.28-−125.61 (m, 1747, calcd for 1H), 4.95-4.71 (m, 3H), 2F) 1700, C₂₅H₃₆F₃NO₆, 4.60-4.46 (m, 0.5H), 1509, 503.2495; 4.25-4.13 (m, 0.5H), 4.04-3.89 (m, 1368, found, 1H), 3.84-3.69 (m, 1H), 1297, 503.2499 3.37-3.18 (m, 3H), 3.03 (dd, J = 13.3, 1080 3.5 Hz, 1H), 2.41-2.30 (m, 1H), 2.19-1.99 (m, 1H), 1.88-1.75 (m, 1H), 1.72-1.32 (m, 17H), 0.93-0.75 (m, 1H) F213 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.05, 2954, (m/z) 7.11-7.01 (m, 2H), 7.01-6.91 (m, −117.18 1734, ([M]⁺) 2H), 5.11-4.73 (m, 4H), 1703, calcd for 4.66-4.50 (m, 0.5H), 1509, C₂₉H₄₂FNO₇, 4.33-4.18 (m, 0.5H), 3.41-3.24 (m, 1368, 535.2945; 3H), 2.85-2.68 (m, 2H), 1297, found, 2.68-2.58 (m, 1H), 2.36 (dd, J = 13.7, 1167 535.2961 11.1 Hz, 1H), 2.22-2.02 (m, 1H), 2.01-1.37 (m, 21H), 1.34-1.20 (m, 3H), 1.03-0.88 (m, 1H) F214 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.05, 2976, (m/z) 7.13-7.01 (m, 2H), 7.02-6.89 (m, −117.17 1737, ([M]⁺) 2H), 5.09-4.74 (m, 4H), 1704, calcd for 4.64-4.52 (m, 0.5H), 1510, C₂₇H₄₀FNO₇, 4.34-4.19 (m, 0.5H), 3.42-3.22 (m, 1367, 509.2789; 3H), 2.71-2.49 (m, 2H), 1297, found, 2.36 (dd, J = 13.8, 11.2 Hz, 1H), 1177 509.2795 2.23-2.01 (m, 1H), 1.98-1.82 (m, 1H), 1.78-1.37 (m, 14H), 1.35-1.13 (m, 8H), 1.03-0.85 (m, 1H) F215 — — HRMS-ESI ¹H NMR (CDCl₃) δ 7.30 (dd, J = 8.7, ¹³C NMR (CDCl₃) δ (m/z) 7.3 Hz, 2H), 7.00 (td, J = 6.3, 173.29, 159.66, ([M]⁺) 3.0 Hz, 4H), 6.96 (t, J = 7.3 Hz, 157.83, 154.89, calcd for 2H), 6.79 (d, J = 8.6 Hz, 132.21, 129.67, C₂₈H₃₇NO₆, 2H), 5.15-4.99 (m, 2H), 121.17, 115.54, 483.2621; 4.30 (t, J = 9.0 Hz, 1H), 113.72, 81.13, 79.90, found, 4.26-4.14 (m, 1H), 3.76 (s, 3H), 74.60, 55.20, 52.94, 483.2600 2.93 (dd, J = 13.5, 3.3 Hz, 45.73, 35.93, 34.14, 1H), 2.28 (dd, J = 13.5, 11.8 Hz, 28.32, 26.72, 18.80, 1H), 2.23-2.16 (m, 1H), 18.40 2.00 (dt, J = 8.3, 3.9 Hz, 1H), 1.64-1.48 (m, 2H), 1.43 (s, 9H), 1.33 (d, J = 6.5 Hz, 3H), 1.15-1.02 (m, 1H), 1.00-0.87 (m, 1H) F216 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ — Film) (m/z) 7.32-7.27 (m, 2H), 6.97-6.90 (m, 2943, ([M]⁺) 3H), 5.14-4.95 (m, 2H), 2868, calcd for 4.24-4.10 (m, 2H), 2.27 (dt, J = 13.6, 1743, C₂₆H₃₉NO₅, 6.9 Hz, 1H), 1706, 445.2828; 1.88-1.73 (m, 3H), 1.74-1.58 (m, 4H), 1492, found, 1.55-1.46 (m, 4H), 1.44 (s, 1366, 445.2845 9H), 1.41-1.34 (m, 2H), 1200, 1.28 (d, J = 6.5 Hz, 3H), 1160 1.24-1.10 (m, 1H), 1.12-0.80 (m, 3H) F217 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 570 7.07-6.97 (m, 2H), 6.86-6.76 (m, 176.26, 173.56, ([M + Na]⁺) 2H), 5.06-4.85 (m, 3H), 157.94, 155.49, 4.77 (d, J = 11.6 Hz, 1H), 3.78 (s, 131.94, 129.59, 3H), 3.38-3.26 (m, 3H), 113.80, 81.21, 75.54, 2.74 (p, J = 8.0 Hz, 1H), 2.61 (dd, J = 13.7, 72.72, 58.52, 55.43, 3.7 Hz, 1H), 2.31 (dd, 55.22, 44.32, 44.04, J = 13.7, 11.1 Hz, 1H), 35.77, 30.09, 30.00, 2.20-2.02 (m, 1H), 1.99-1.52 (m, 29.58, 28.20, 26.48, 12H), 1.51-1.40 (m, 9H), 25.72, 25.70, 19.09, 1.27 (d, J = 5.8 Hz, 3H), 17.56 1.15-1.04 (m, 1H), 1.00 (t, J = 7.5 Hz, 1H), 0.97-0.87 (m, 1H) F218 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −89.52, m/z 566 7.10-7.00 (m, 2H), 6.88-6.76 (m, −89.56 (d, J = 72.5 Hz) ([M + Na]⁺) 2H), 4.97-4.82 (m, 2H), 4.81-4.71 (m, 1H), 4.55 (s, 1H), 4.19 (t, J = 9.6 Hz, 1H), 3.97-3.84 (m, 1H), 3.78 (s, 3H), 3.72 (dt, J = 9.1, 6.8 Hz, 1H), 3.37-3.26 (m, 3H), 3.14 (td, J = 8.9, 3.2 Hz, 1H), 2.97 (dd, J = 13.4, 3.5 Hz, 1H), 2.37-2.24 (m, 1H), 2.26-2.02 (m, 3H), 1.81-1.57 (m, 5H), 1.58-1.23 (m, 14H), 0.89-0.77 (m, 1H) F219 — — HRMS-ESI ¹H NMR (CDCl₃) δ 5.05 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 4.94-4.77 (m, 173.37, 154.92, 84.35, ([M]⁺) 1H), 4.14 (q, J = 8.1 Hz, 1H), 79.79, 78.53, 75.28, calcd for 3.48 (dd, J = 9.6, 7.0 Hz, 1H), 52.97, 42.26, 37.26, C₂₄H₄₁NO₅, 3.34 (dd, J = 9.6, 6.9 Hz, 1H), 36.86, 34.29, 33.95, 423.2985; 2.97 (t, J = 8.9 Hz, 1H), 31.82, 28.34, 27.59, found, 2.21 (dt, J = 13.6, 7.0 Hz, 1H), 25.10, 25.07, 18.87, 423.2998 1.94-1.64 (m, 5H), 1.64-1.47 (m, 18.11, 11.13, 3.14, 9H), 1.43 (s, 9H), 1.40 (d, J = 6.4 Hz, 2.94 2H), 1.19-0.98 (m, 4H), 0.91 (dd, J = 15.2, 7.9 Hz, 1H), 0.59-0.46 (m, 2H), 0.26-0.08 (m, 2H) F220 — — HRMS-ESI ¹H NMR (CDCl₃) δ 7.07 (dd, J = 8.7, ¹³C NMR (CDCl₃) δ (m/z) 3.3 Hz, 2H), 173.39, 157.80, ([M]⁺) 6.86-6.77 (m, 2H), 4.92-4.73 (m, 2H), 132.82, 129.69, calcd for 4.23-4.11 (m, 1H), 113.73, 83.74, 80.58, C₂₈H₄₅NO₇, 3.81-3.76 (m, 3H), 3.54 (ddd, J = 8.5, 55.25, 46.32, 46.28, 507.3196; 6.3, 2.3 Hz, 1H), 35.76, 30.07, 29.26, found, 3.36-3.25 (m, 3H), 3.10 (td, J = 9.2, 28.38, 28.32, 28.25, 507.3173 3.1 Hz, 1H), 3.03 (dt, J = 13.4, 28.19, 26.54, 19.56, 3.6 Hz, 1H), 2.91 (s, 1H), 19.50, 19.25, 19.12, 2.33-2.20 (m, 1H), 1.89 (dp, J = 13.3, 18.26, 18.18 6.8 Hz, 1H), 1.77 (s, 1H), 1.67-1.47 (m, 3H), 1.47-1.37 (m, 15H), 0.96 (t, J = 6.3 Hz, 6H), 0.85-0.76 (m, 1H) F221 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 7.12-7.03 (m, 2H), 6.86-6.77 (m, 173.30, 157.80, ([M]⁺) 2H), 4.89-4.73 (m, 3H), 132.75, 129.69, calcd for 4.28-4.11 (m, 1H), 3.78 (s, 3H), 113.73, 99.98, 88.37, C₂₇H₄₃NO₇, 3.71 (dtd, J = 8.4, 6.6, 1.8 Hz, 84.02, 83.98, 83.86, 493.3040; 1H), 3.50 (dtd, J = 8.5, 6.7, 1.7 Hz, 81.11, 75.59, 75.52, found, 1H), 3.30 (d, J = 14.0 Hz, 55.25, 46.20, 46.12, 493.3018 3H), 3.12 (td, J = 8.9, 3.7 Hz, 35.86, 35.82, 28.32, 1H), 3.02 (dd, J = 13.4, 3.3 Hz, 28.23, 26.56, 23.59, 1H), 2.27 (ddd, J = 13.3, 19.21, 18.68, 18.18, 11.7, 6.2 Hz, 1H), 1.76 (s, 1H), 18.12, 10.75 1.71-1.50 (m, 5H), 1.44 (dd, J = 10.8, 4.6 Hz, 14H), 0.97 (dd, J = 7.8, 6.9 Hz, 3H), 0.81 (s, 1H) F222 — — ESIMS ¹H NMR (CDCl₃) δ 7.29 (dd, J = 1.8, ¹³C NMR (CDCl₃) δ m/z 446.2 0.9 Hz, 1H), 6.27 (dd, J = 3.1, 173.31, 154.91, [(M + Na)⁺] 1.9 Hz, 1H), 6.00 (d, J = 3.2 Hz, 154.68, 140.98, 1H), 5.05 (d, J = 8.3 Hz, 110.07, 106.00, 83.49, 1H), 4.87 (dq, J = 9.3, 6.1 Hz, 80.24, 75.08, 52.92, 1H), 4.20-4.09 (m, 1H), 43.13, 34.10, 32.07, 3.48 (dd, J = 8.4, 6.5 Hz, 1H), 29.32, 29.19, 28.33, 3.28 (dd, J = 8.4, 6.4 Hz, 1H), 26.23, 22.01, 19.47, 3.10 (t, J = 9.0 Hz, 1H), 19.46, 18.78, 18.18 2.99 (dd, J = 14.5, 3.5 Hz, 1H), 2.48 (dd, J = 14.7, 11.3 Hz, 1H), 2.16 (dt, J = 13.5, 6.8 Hz, 1H), 1.88 (tdd, J = 16.7, 9.0, 3.6 Hz, 3H), 1.66 (dt, J = 11.8, 2.8 Hz, 1H), 1.53-1.47 (m, 1H), 1.43 (s, 9H), 1.46-1.40 (m, 4H), 1.10 (dt, J = 13.8, 10.8 Hz, 1H), 0.93 (d, J = 6.7 Hz, 6H) F223 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 506 5.03-4.74 (m, 3H), 4.30-4.17 (m, 182.04, 173.67, 36.98, ([M + Na]⁺) 1H), 3.39-3.30 (m, 3H), 36.48, 35.09, 34.30, 2.72-2.51 (m, 1H), 2.22-2.04 (m, 33.68, 31.84, 28.24, 1H), 1.88-0.75 (m, 36H) 28.18, 25.04, 25.02, 22.53, 19.13, 18.95, 18.84, 18.79, 18.29, 17.51 F224 144-145 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 400.2 7.32-7.24 (m, 2H), 6.94 (dd, J = 7.8, 173.36, 159.67, [(M + Na)⁺] 6.5 Hz, 3H), 5.05 (m, 2H), 154.90, 129.57, 4.20 (dt, J = 10.8, 7.7 Hz, 1H), 120.98, 115.47, 82.27, 4.13 (t, J = 8.8 Hz, 1H), 79.86, 74.59, 53.05, 2.27 (dt, J = 12.8, 6.2 Hz, 1H), 37.61, 34.14, 32.37, 1.90 (d, J = 7.0 Hz, 1H), 28.33, 19.15, 18.31, 1.74-1.53 (m, 4H), 1.44 (s, 9H), 17.74 1.30 (d, J = 6.5 Hz, 3H), 1.25-1.17 (m, 1H), 0.99 (d, J = 6.9 Hz, 3H) F225 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 292.2 7.50-7.04 (m, 5H), 5.06 (d, J = 7.9 Hz, 173.39, 154.94, [(M − tBoc + H)⁺] 1H), 4.90 (m, 1H), 4.70 (d, 128.46, 127.81, J = 10.8 Hz, 1H), 4.58 (d, J = 10.8 Hz, 127.73, 85.30, 79.81, 1H), 4.16 (m, 1H), 75.57, 75.09, 53.01, 3.19 (t, J = 8.9 Hz, 1H), 37.92, 34.22, 32.29, 2.31-2.14 (m, 1H), 1.83-1.67 (m, 28.34, 19.01, 18.23, 1H), 1.66-1.58 (m, 3H), 17.77 1.46 (d, J = 6.4 Hz, 3H), 1.44 (s, 9H), 1.23-1.08 (m, 2H), 1.06 (d, J = 6.8 Hz, 3H) F226 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 500.3 7.31-7.26 (m, 2H), 7.23-7.15 (m, 171.03, 152.84, ([M + Na]⁺) 3H), 4.80 (dd, J = 10.6, 7.9 Hz, 140.62, 128.88, 1H), 4.71 (dq, J = 9.4, 6.3 Hz, 128.47, 126.06, 82.69, 1H), 3.50 (t, J = 9.0 Hz, 76.09, 74.83, 57.42, 1H), 3.11 (dd, J = 13.4, 4.6 Hz, 47.48, 37.80, 30.66, 1H), 2.47 (dd, J = 13.5, 27.96, 27.34, 19.75, 10.4 Hz, 1H), 2.30-2.20 (m, 18.25 1H), 1.98 (dddd, J = 13.1, 7.8, 5.2, 2.2 Hz, 1H), 1.76 (ddd, J = 10.1, 8.3, 4.5 Hz, 1H), 1.60 (dd, J = 10.3, 6.5 Hz, 2H), 1.54-1.45 (m, 20H), 1.45-1.39 (m, 2H), 1.26 (t, J = 7.1 Hz, 2H) F227 — — ESIMS ¹H NMR (300 MHz, CDCl₃) δ ¹³C NMR (75 MHz, m/z 458.3 7.31-7.20 (m, 2H), CDCl₃) δ 173.40, ([M + Na]⁺) 7.19-7.07 (m, 3H), 5.12-4.98 (m, 155.11, 140.95, 1H), 4.88 (dq, J = 9.0, 6.4 Hz, 129.06, 128.50, 1H), 4.20-4.05 (m, 1H), 128.46, 126.06, 84.91, 3.91 (ddd, J = 10.0, 5.7, 3.9 Hz, 79.94, 75.12, 72.99, 1H), 3.74-3.62 (m, 1H), 72.34, 59.25, 53.09, 3.60-3.48 (m, 2H), 3.37 (s, 3H), 45.97, 36.94, 34.30, 3.24-3.05 (m, 3H), 2.31 (dd, 28.52, 26.78, 18.91, J = 13.2, 11.6 Hz, 1H), 18.38 2.20-2.05 (m, 1H), 1.92-1.75 (m, 1H), 1.45 (d, J = 6.5 Hz, 3H), 1.40 (s, 9H), 1.55-1.30 (m, 2H, overlapping), 1.01 (q, J = 11.6 Hz, 1H), 0.84-0.68 (m, 1H) F229 108-110 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 504 7.41-7.26 (m, 5H), 7.07 (d, J = 7.9 Hz, 173.32, 154.95, ([M + Na]⁺) 2H), 7.02 (d, J = 8.0 Hz, 137.92, 137.48, 2H), 5.04 (d, J = 8.3 Hz, 1H), 135.38, 129.06, 4.94 (dq, J = 9.2, 6.5 Hz, 1H), 128.73, 128.56, 4.79 (d, J = 10.8 Hz, 1H), 127.94, 127.77, 84.20, 4.63 (d, J = 10.8 Hz, 1H), 4.17 (dt, 79.83, 75.73, 75.03, J = 10.8, 7.5 Hz, 1H), 3.35 (t, J = 9.0 Hz, 52.94, 45.88, 36.40, 1H), 3.10 (dd, J = 13.3, 34.18, 28.36, 26.68, 3.3 Hz, 1H), 2.32 (dd, J = 13.3, 21.04, 18.76, 18.33 11.8 Hz, 1H), 2.30 (s, 3H), 2.22-2.11 (m, 1H), 1.89 (ddt, J = 12.1, 8.3, 3.8 Hz, 1H), 1.64-1.33 (m, 15H), 1.04 (qd, J = 10.5, 5.5 Hz, 1H), 0.88-0.77 (m, 1H) F230 164-166 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 605 7.41-7.26 (m, 5H), 7.07 (d, J = 8.1 Hz, 171.13, 152.83, ([M + Na]⁺) 2H), 7.03 (d, J = 8.0 Hz, 137.98, 137.51, 2H), 4.88-4.75 (m, 3H), 135.31, 129.01, 4.61 (d, J = 10.8 Hz, 1H), 3.35 (t, J = 9.1 Hz, 128.77, 128.54, 1H), 3.10 (dd, J = 13.3, 127.89, 127.76, 84.14, 3.3 Hz, 1H), 82.64, 75.44, 75.21, 2.40-2.28 (m, 4H), 2.22 (tt, J = 13.5, 7.2 Hz, 57.57, 45.77, 36.43, 1H), 2.02-1.88 (m, 2H), 30.83, 27.97, 26.84, 1.64-1.41 (m, 24H), 21.04, 19.67, 18.49 0.96-0.84 (m, 1H) F231 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 454.4 7.34-7.23 (m, 2H), 7.23-7.11 (m, 173.26, 154.91, ([M + Na]⁺) 3H), 5.02 (d, J = 8.3 Hz, 1H), 140.72, 128.86, 4.88 (dq, J = 9.2, 6.4 Hz, 1H), 128.34, 125.90, 83.80, 4.14 (ddt, J = 14.3, 8.9, 7.1 Hz, 79.79, 78.74, 75.13, 1H), 3.57 (dd, J = 9.7, 7.0 Hz, 52.87, 45.98, 36.85, 1H), 3.44 (dd, J = 9.7, 6.8 Hz, 34.17, 31.59, 28.31, 1H), 3.21-3.08 (m, 2H), 26.62, 25.28, 22.65, 2.32 (dd, J = 13.3, 11.7 Hz, 1H), 18.65, 18.12, 14.12, 2.21-2.07 (m, 1H), 1.86 (tdd, 11.16, 3.16, 3.00 J = 12.1, 6.7, 2.7 Hz, 1H), 1.66-1.25 (m, 18H), 1.17-0.99 (m, 2H), 0.84-0.75 (m, 1H), 0.65-0.53 (m, 2H), 0.24 (dtt, J = 4.9, 3.5, 1.8 Hz, 2H) F232 110-114 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 570 7.12-7.03 (m, 4H), 4.82-4.69 (m, 171.12, 152.82, ([M + Na]⁺) 2H), 3.52 (dd, J = 8.4, 6.3 Hz, 137.73, 135.23, 1H), 3.30 (dd, J = 8.4, 6.5 Hz, 128.98, 128.75, 83.64, 1H), 3.11 (t, J = 9.1 Hz, 1H), 82.58, 80.32, 75.37, 3.05 (dd, J = 13.2, 3.2 Hz, 57.55, 46.00, 36.25, 1H), 2.36-2.13 (m, 5H), 30.81, 29.26, 27.96, 2.01-1.77 (m, 3H), 1.48 (s, 24H), 26.73, 21.02, 19.65, 0.96 (d, J = 6.7 Hz, 3H), 19.56, 19.51, 18.36 0.95 (d, J = 6.7 Hz, 3H), 0.91-0.79 (m, 1H) F233 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 456.4 7.32-7.23 (m, 2H), 7.22-7.12 (m, 173.30, 154.92, ([M + Na]⁺) 3H), 5.01 (d, J = 8.3 Hz, 1H), 140.86, 128.84, 4.87 (dq, J = 9.3, 6.4 Hz, 1H), 128.32, 125.87, 83.71, 4.24-4.05 (m, 1H), 3.55 (dd, 80.65, 79.81, 75.19, J = 8.4, 6.2 Hz, 1H), 3.32 (dd, 52.88, 46.10, 36.70, J = 8.4, 6.5 Hz, 1H), 34.19, 29.70, 29.26, 3.17-3.03 (m, 2H), 2.31 (dd, J = 13.2, 28.32, 26.60, 19.54, 11.8 Hz, 1H), 2.16 (dt, J = 13.1, 19.49, 18.73, 18.19 6.8 Hz, 1H), 1.95-1.69 (m, 3H), 1.61-1.48 (m, 3H), 1.43-1.39 (m, 11H), 0.96 (dd, J = 6.8, 5.1 Hz, 6H), 0.90-0.73 (m, 2H) F234 — — ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ m/z 418.3 1H), 4.91-4.78 (m, 173.34, 99.99, 83.94, ([M + H]⁺) 1H), 4.15 (d, J = 11.0 Hz, 1H), 80.39, 75.25, 52.96, 3.44 (dd, J = 8.4, 6.6 Hz, 1H), 42.21, 34.10, 32.15, 3.25 (dd, J = 8.3, 6.5 Hz, 1H), 29.93, 29.19, 28.33, 3.00 (t, J = 8.7 Hz, 1H), 19.48, 18.89, 18.15, 2.57 (ddd, J = 14.3, 9.7, 4.6 Hz, 15.37 1H), 2.42 (ddd, J = 12.8, 9.1, 7.2 Hz, 1H), 2.27-2.15 (m, 1H), 2.09 (s, 3H), 1.93 (d, J = 7.0 Hz, 1H), 1.87-1.77 (m, 1H), 1.74-1.59 (m, 3H), 1.54-1.46 (m, 2H), 1.44 (s, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.26-1.10 (m, 1H), 0.95 (s, 1H), 0.95-0.89 (m, 6H) F235 — — ESIMS ¹H NMR (CDCl₃) δ 5.07 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 412.3 1H), 4.92-4.78 (m, 173.30, 154.91, 83.83, [(M + Na)⁺] 1H), 4.55 (td, J = 5.6, 3.2 Hz, 83.78, 82.14, 80.21, 1H), 4.47-4.37 (m, 1H), 79.82, 75.14, 52.97, 4.15 (dt, J = 10.7, 7.8 Hz, 1H), 39.75, 34.06, 31.57, 3.43 (dd, J = 8.4, 6.6 Hz, 1H), 31.37, 29.15, 28.69, 3.24 (dd, J = 8.4, 6.4 Hz, 1H), 28.32, 19.44, 19.40, 3.09-2.96 (m, 1H), 2.22 (dt, J = 13.4, 19.07, 18.14 6.7 Hz, 1H), 2.10-1.95 (m, 1H), 1.83 (dp, J = 13.2, 6.6 Hz, 1H), 1.67 (d, J = 7.9 Hz, 3H), 1.64-1.53 (m, 2H), 1.44 (s, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.17 (q, J = 11.6 Hz, 1H), 1.08-0.97 (m, 1H), 0.94-0.88 (m, 6H) F236 86-89 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 468 7.11-7.02 (m, 4H), 5.02 (d, J = 8.3 Hz, 173.21, 154.85, ([M + Na]⁺) 1H), 4.94-4.81 (m, 1H), 137.49, 135.27, 4.14 (dt, J = 10.9, 7.5 Hz, 1H), 128.97, 128.66, 83.74, 3.56 (dd, J = 9.7, 7.0 Hz, 1H), 79.72, 78.68, 75.09, 3.43 (dd, J = 9.7, 6.8 Hz, 1H), 52.81, 36.30, 34.13, 3.13 (t, J = 9.1 Hz, 1H), 28.26, 26.50, 20.96, 3.08 (dd, J = 13.3, 3.4 Hz, 1H), 18.57, 18.06, 11.11, 2.35-2.23 (m, 4H), 2.15 (dt, J = 12.8, 3.10, 2.94 6.7 Hz, 1H), 1.83 (ddd, J = 12.1, 8.4, 3.9 Hz, 1H), 1.60-1.34 (m, 15H), 1.18-0.96 (m, 2H), 0.85-0.72 (m, 1H), 0.61-0.54 (m, 2H), 0.28-0.20 (m, 2H) F237 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (75 MHz, m/z 452.0 7.31-7.24 (m, 2H), 7.23-7.12 (m, CDCl₃) δ 171.29, ([M + Na]⁺) 3H), 4.84-4.69 (m, 1H), 153.02, 141.05, 3.70 (dt, J = 8.7, 6.6 Hz, 1H), 129.09, 128.60, 3.49 (dt, J = 8.6, 6.7 Hz, 1H), 126.29, 126.02, 84.17, 3.21-3.02 (m, 2H), 2.89 (t, J = 7.6 Hz, 82.76, 75.54, 75.47, 1H), 2.71 (dd, J = 8.2, 7.0 Hz, 57.79, 46.07, 44.69, 1H), 2.34 (dd, J = 13.3, 37.08, 31.02, 29.95, 11.7 Hz, 1H), 2.21 (ddt, J = 13.5, 28.17, 27.13, 23.82, 10.6, 7.3 Hz, 1H), 19.91, 18.52, 10.97 2.01-1.77 (m, 2H), 1.70-1.53 (m, 4H), 1.48 (s, 18H), 1.44 (d, J = 6.4 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H), 0.92-0.79 (m, 1H) F238 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 468.2 7.31-7.23 (m, 2H), 7.23-7.12 (m, 171.38, 152.94, ([M − Boc + Na]⁺) 3H), 4.82-4.65 (m, 1H), 141.10, 128.59, 4.16-4.06 (m, 1H), 3.30-3.13 (m, 128.57, 128.41, 1H), 2.88 (t, J = 7.6 Hz, 1H), 126.21, 125.88, 83.83, 2.75-2.66 (m, 1H), 82.67, 82.53, 75.93, 2.37-2.23 (m, 1H), 2.20-2.10 (m, 57.91, 45.36, 44.61, 0H), 1.98-1.87 (m, 1H), 39.36, 37.03, 32.98, 1.83-1.66 (m, 4H), 1.61-1.53 (m, 32.69, 30.89, 29.84, 2H), 1.48 (s, 9H), 1.44 (d, J = 9.0 Hz, 28.06, 23.15, 23.09, 2H), 0.99-0.80 (m, 20.10, 18.68 1H) F239 — — HRMS-ESI ¹H NMR (CDCl₃) δ 7.07 (d, J = 8.6 Hz, ¹³C NMR (CDCl₃) δ (m/z) 2H), 6.82 (d, J = 8.6 Hz, 173.28, 157.83, ([M]⁺) 2H), 5.00 (d, J = 8.4 Hz, 132.68, 129.72, calcd for 1H), 4.88 (dd, J = 9.1, 6.3 Hz, 113.76, 83.81, 79.82, C₂₆H₃₉NO₆, 1H), 4.21-4.08 (m, 1H), 78.76, 75.16, 55.24, 461.2777; 3.78 (s, 3H), 3.56 (dd, J = 9.7, 7.0 Hz, 52.88, 46.11, 35.89, found, 1H), 3.43 (dd, J = 9.6, 6.8 Hz, 34.22, 28.32, 26.57, 261.2757 1H), 3.13 (t, J = 9.1 Hz, 18.64, 18.11, 11.17, 1H), 3.06 (dd, J = 13.4, 3.4 Hz, 3.16, 2.99 1H), 2.26 (dd, J = 13.4, 11.7 Hz, 1H), 2.22-2.07 (m, 1H), 1.91-1.74 (m, 1H), 1.61-1.34 (m, 15H), 1.20-1.08 (m, 1H), 1.03 (q, J = 11.7 Hz, 1H), 0.98-0.71 (m, 1H), 0.65-0.48 (m, 2H), 0.27-0.15 (m, 2H) F240 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 484.3 7.35-7.12 (m, 4H), 6.93 (p, J = 7.4 Hz, 173.28, 159.34, ([M + H]⁺) 4H), 6.86-6.76 (m, 2H), 158.76, 129.68, 5.15-4.98 (m, 2H), 129.39, 121.17, 4.33-4.15 (m, 2H), 3.94 (t, J = 6.6 Hz, 120.61, 115.40, 2H), 2.33-2.21 (m, 1H), 114.42, 99.98, 81.14, 2.06 (dd, J = 16.4, 4.9 Hz, 74.68, 66.01, 53.01, 2H), 1.93 (d, J = 12.6 Hz, 1H), 40.14, 34.11, 30.49, 1.89-1.79 (m, 1H), 28.33, 24.93, 19.20, 1.79-1.65 (m, 1H), 1.62 (d, J = 14.8 Hz, 18.35 1H), 1.44 (s, 9H), 1.31 (d, J = 6.5 Hz, 3H), 1.19 (dd, J = 25.8, 13.7 Hz, 2H) F241 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 476.4 7.35-7.20 (m, 5H), 7.19-7.13 (m, 173.32, 159.66, ([M + Na]⁺) 1H), 7.13-7.07 (m, 2H), 154.93, 140.25, 7.05-6.93 (m, 2H), 5.08 (dt, J = 9.2, 136.31, 129.70, 3.4 Hz, 2H), 4.77 (d, J = 2.6 Hz, 128.80, 128.32, 1H), 4.37 (qt, J = 5.6, 125.97, 121.22, 3.6 Hz, 1H), 4.31 (t, J = 9.0 Hz, 115.54, 81.14, 79.91, 1H), 4.27-4.15 (m, 1H), 74.60, 45.62, 36.87, 3.00 (dd, J = 13.3, 3.3 Hz, 34.11, 28.33, 26.76, 1H), 2.33 (dd, J = 13.4, 11.8 Hz, 18.83, 18.41 1H), 2.27-2.15 (m, 1H), 2.12-2.01 (m, 1H), 1.93-1.78 (m, 1H), 1.43 (s, 9H), 1.34 (d, J = 6.5 Hz, 3H), 1.16-1.04 (m, 1H), 1.01-0.84 (m, 1H) F242 — — ESIMS ¹H NMR (CDCl₃) δ 7.27 (t, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 422.3 2H), 6.94 (dd, J = 7.7, 173.28, 159.46, ([M + H]⁺) 3.3 Hz, 3H), 5.10 (d, J = 8.1 Hz, 154.90, 129.61, 1H), 5.08-4.98 (m, 1H), 121.05, 115.38, 81.12, 4.20 (q, J = 7.9, 6.9 Hz, 2H), 79.86, 74.71, 70.79, 3.36 (t, J = 6.5 Hz, 2H), 58.42, 52.99, 40.09, 3.25 (s, 3H), 2.27 (dt, J = 13.3, 6.8 Hz, 34.12, 30.53, 28.33, 1H), 1.88 (ddt, J = 10.8, 28.15, 19.07, 18.36 6.9, 3.9 Hz, 2H), 1.83-1.71 (m, 1H), 1.70-1.61 (m, 1H), 1.60-1.52 (m, 1H), 1.44 (s, 10H), 1.28 (d, J = 6.5 Hz, 3H), 1.25-1.16 (m, 1H), 1.16-1.05 (m, 1H) F243 — — ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ m/z 402.3 1H), 4.83 (dq, J = 12.9, 173.35, 154.92, 84.01, ([M + H]⁺) 6.4 Hz, 1H), 80.35, 79.80, 75.29, 4.22-4.08 (m, 1H), 3.45-3.35 (m, 3H), 71.28, 58.50, 52.96, 3.31 (s, 3H), 3.31-3.22 (m, 40.24, 34.17, 30.37, 1H), 3.01 (t, J = 8.8 Hz, 1H), 29.16, 28.33, 19.51, 2.21 (dt, J = 13.1, 6.4 Hz, 1H), 19.42, 18.99, 18.16 1.94 (dtd, J = 11.1, 7.6, 3.4 Hz, 1H), 1.83 (dp, J = 13.3, 6.7 Hz, 1H), 1.63 (dd, J = 16.5, 6.0 Hz, 2H), 1.54 (d, J = 7.7 Hz, 1H), 1.43 (s, 11H), 1.40 (d, J = 6.4 Hz, 3H), 1.23-1.10 (m, 1H), 1.02-0.94 (m, 1H), 0.91 (dd, J = 6.7, 2.7 Hz, 6H) F244 63-68 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 490 7.36-7.26 (m, 2H), 7.06 (d, J = 7.8 Hz, 173.24, 159.65, ([M + Na]⁺) 2H), 7.04-6.94 (m, 5H), 154.86, 137.04, 5.14-5.02 (m, 2H), 4.31 (t, J = 8.9 Hz, 135.36, 129.63, 1H), 4.21 (dt, J = 11.0, 128.97, 128.62, 7.6 Hz, 1H), 2.97 (dd, J = 13.4, 121.14, 115.52, 81.13, 3.2 Hz, 1H), 79.83, 74.56, 52.91, 2.36-2.17 (m, 5H), 2.11-2.00 (m, 45.59, 36.35, 34.09, 1H), 1.67-1.41 (m, 12H), 28.29, 26.68, 20.97, 1.34 (d, J = 6.5 Hz, 3H), 18.76, 18.37 1.16-1.02 (m, 1H), 1.00-0.86 (m, 1H) F245 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2952, (m/z) 7.33-7.21 (m, 2H), 6.99-6.84 (m, 1752, [M + H]⁺ 3H), 5.10-4.78 (m, 3H), 1705, calcd for 4.65-4.51 (m, 0.5H), 1597, C₂₇H₄₃NO₆, 4.30-4.10 (m, 1.5H), 3.42-3.29 (m, 1493, 477.3090; 3H), 2.24-2.02 (m, 1H), 1367, found, 1.92-1.33 (m, 16H), 1.28 (d, J = 6.4 Hz, 1297, 477.3086 3H), 1.26-0.99 (m, 1174 3H), 0.80 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.5 Hz, 3H), 0.77-0.69 (m, 1H) F246 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2954, (m/z) 5.03-4.66 (m, 4H), 4.60-4.47 (m, 1747, [M + H]⁺ 0.5H), 4.40-4.12 (m, 0.5H), 1704, calcd for 3.53-3.19 (m, 5H), 1454, C₂₅H₄₇NO₆, 2.19-1.42 (m, 18H), 1.40 (d, J = 6.4 Hz, 1366, 457.3403; 3H), 1.31-1.04 (m, 3H), 1296, found, 0.99-0.81 (m, 13H) 1174, 457.3417 1143, 1084 F247 ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ m/z, 372.3 1H), 4.83 (dd, J = 9.2, 173.40, 84.22, 80.41, ([M + H]⁺) 6.5 Hz, 1H), 79.77, 75.35, 52.97, 4.25-4.05 (m, 1H), 3.41 (dd, J = 8.4, 6.6 Hz, 45.17, 34.26, 29.17, 1H), 3.25 (dd, J = 8.3, 6.5 Hz, 28.34, 27.10, 23.22, 1H), 2.98 (t, J = 8.9 Hz, 19.49, 19.45, 18.70, 1H), 2.21 (dt, J = 12.4, 6.2 Hz, 18.20, 11.94 1H), 1.83 (dp, J = 13.2, 6.7 Hz, 1H), 1.70 (dt, J = 9.7, 4.7 Hz, 2H), 1.51 (dd, J = 15.4, 7.4 Hz, 1H), 1.44 (s, 10H), 1.39 (d, J = 6.4 Hz, 5H), 1.25-1.10 (m, 2H), 0.99-0.83 (m, 9H) F248 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 502 7.43-7.27 (m, 5H), 7.12-7.03 (m, 173.22, 161.33 (dd, J = 246.9, ([M − H]⁻) 1H), 6.82-6.72 (m, 2H), 12.2 Hz), 5.03 (d, J = 8.3 Hz, 1H), 4.95 (dq, J = 9.1, 161.09 (dd, J = 246.2, 6.4 Hz, 1H), 4.80 (d, J = 10.9 Hz, 10.5 Hz), 154.89, 1H), 4.63 (d, J = 10.9 Hz, 137.75, 131.52 (dd, J = 9.0, 1H), 4.18 (dt, J = 10.9, 7.5 Hz, 7.0 Hz), 128.50, 1H), 3.38 (t, J = 9.0 Hz, 127.89, 127.63, 1H), 3.07-2.96 (m, 1H), 123.13 (dd, J = 15.4, 3.3 Hz), 2.49 (dd, J = 13.5, 11.6 Hz, 1H), 111.02 (dd, J = 20.9, 2.19 (dt, J = 13.1, 6.9 Hz, 1H), 3.7 Hz), 1.98-1.85 (m, 1H), 104.18-103.18 (m), 83.93, 1.72-1.32 (m, 15H), 1.14-0.99 (m, 79.83, 75.36, 74.84, 1H), 0.94-0.82 (m, 1H) 52.87, 44.42, 34.05, 29.26, 28.29, 27.17, 18.75, 18.24 ¹⁹F NMR (CDCl₃) δ −113.33 (d, J = 6.7 Hz), −113.62 (d, J = 6.7 Hz) F249 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 7.39-7.27 (m, 2H), 7.03-6.82 (m, 173.20, 159.18, [M + Na]⁺ 3H), 5.18-4.99 (m, 2H), 154.89, 129.74, calcd for 4.21 (q, J = 8.7 Hz, 2H), 3.44 (ddd, 121.33, 115.37, 80.94, C₂₂H₃₂BrNNaO₅, J = 10.0, 7.4, 5.0 Hz, 1H), 79.95, 74.57, 53.02, 492.1356; 3.33 (ddd, J = 9.9, 8.4, 6.9 Hz, 1H), 41.18, 34.13, 33.95, found, 2.28 (dt, J = 13.0, 6.6 Hz, 1H), 31.54, 28.33, 19.13, 492.1352 2.10 (dtd, J = 12.6, 7.9, 4.5 Hz, 18.29 1H), 2.05-1.96 (m, 1H), 1.85-1.73 (m, 2H), 1.73-1.61 (m, 1H), 1.44 (s, 10H), 1.30 (d, J = 6.5 Hz, 3H), 1.28-1.20 (m, 1H), 1.20-1.09 (m, 1H) F250 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 392.3 7.38-7.16 (m, 2H), 7.00-6.87 (m, 173.34, 159.68, [(M + H)+] 3H), 5.19-4.97 (m, 2H), 154.91, 129.58, 4.18 (t, J = 8.8 Hz, 2H), 2.27 (dt, J = 13.1, 120.95, 115.40, 81.44, 6.7 Hz, 1H), 79.86, 74.74, 53.00, 1.91-1.77 (m, 1H), 1.70-1.58 (m, 44.96, 34.20, 28.34, 3H), 1.58-1.48 (m, 1H), 27.85, 27.03, 26.85, 1.44 (s, 9H), 1.28 (d, J = 6.5 Hz, 23.50, 18.74, 18.40, 3H), 1.25-1.14 (m, 2H), 17.53, 13.61, 11.86 1.12-1.01 (m, 1H), 0.86 (t, J = 7.3 Hz, 3H) F251 — — ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 440.4 1H), 4.84 (dq, J = 12.9, 173.29, 154.90, ([M + H]⁺) 6.4 Hz, 1H), 4.14 (dt, J = 10.6, 121.90, 84.01, 79.78, 7.7 Hz, 1H), 78.35, 75.44, 75.22, 3.49-3.37 (m, 4H), 3.25 (dt, J = 6.8, 3.2 Hz, 69.10, 52.93, 40.47, 2H), 3.04 (t, J = 8.8 Hz, 34.18, 30.66, 28.32, 1H), 2.28-2.15 (m, 1H), 18.92, 18.09, 11.08, 1.98 (dtd, J = 10.7, 7.5, 3.1 Hz, 10.64, 3.16, 3.00, 2.93, 1H), 1.71-1.55 (m, 3H), 2.87 1.55-1.46 (m, 2H), 1.43 (s, 9H), 1.41 (d, J = 6.4 Hz, 3H), 1.23-1.10 (m, 1H), 1.05 (dddd, J = 14.9, 10.0, 5.9, 2.4 Hz, 2H), 1.00-0.90 (m, 1H), 0.60-0.45 (m, 4H), 0.25-0.15 (m, 4H) F253 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 626 7.41-7.27 (m, 5H), 7.09 (td, J = 8.7, 171.04, 161.32 (dd, J = 246.7, ([M + Na]⁺) 6.8 Hz, 1H), 6.82-6.71 (m, 12.2 Hz), 2H), 4.87-4.76 (m, 2H), 162.52-159.74 (m), 4.61 (d, J = 10.9 Hz, 1H), 3.37 (t, J = 9.1 Hz, 152.83, 137.85, 1H), 3.06-2.96 (m, 131.74-131.38 (m), 128.50, 1H), 2.50 (dd, J = 13.5, 11.6 Hz, 127.87, 127.65, 1H), 2.31-2.16 (m, 1H), 123.51-122.90 (m), 2.03-1.89 (m, 1H), 111.34-110.66 (m), 103.61 (t, 1.70-1.39 (m, 26H), 1.02-0.91 (m, J = 25.7 Hz), 83.90, 1H) 82.65, 75.04, 75.02, 57.50, 44.32, 30.74, 29.22, 27.95, 27.43, 19.71, 18.43 ¹⁹F NMR (CDCl₃) δ −113.52 (d, J = 6.8 Hz), −113.69 (d, J = 6.5 Hz) F254 108-115 — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ m/z 570 7.41-7.27 (m, 5H), 7.07 (td, J = 8.7, −113.13-−113.46 (m), ([M + Na]⁺) 6.4 Hz, 1H), 6.82-6.70 (m, −113.58-−113.82 (m) 2H), 5.01-4.85 (m, 2H), 4.80 (d, J = 10.9 Hz, 2H), 4.62 (d, J = 10.9 Hz, 1.5H), 4.29-4.15 (m, 0.5H), 3.45-3.25 (m, 4H), 3.08-2.91 (m, 1H), 2.50 (t, J = 12.5 Hz, 1H), 2.21-2.02 (m, 1H), 2.00-1.86 (m, 1H), 1.78-1.34 (m, 16H), 1.00-0.83 (m, 1H) F255 — — ESIMS ¹H NMR (CDCl₃) δ 7.09 (dd, J = 8.0, ¹⁹F NMR (CDCl₃) δ −66.37 m/z 563 3.1 Hz, 2H), 7.03 (dd, J = 8.0, ([M + NH₄]⁺) 3.3 Hz, 2H), 4.97-4.66 (m, 3H), 3.78 (dd, J = 9.4, 5.3 Hz, 1H), 3.58 (dt, J = 8.8, 6.2 Hz, 1H), 3.30 (d, J = 14.2 Hz, 1H), 3.22-3.07 (m, 1H), 2.99-2.84 (m, 3H), 2.70 (dd, J = 8.2, 7.0 Hz, 1H), 2.40-2.12 (m, 6H), 1.93-1.73 (m, 4H), 1.73-1.35 (m, 16H), 0.90-0.75 (m, 1H) F256 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ m/z 598 7.36-7.05 (m, 6H), 6.85-6.71 (m, −113.14-−113.49 (m), ([M + H]⁺) 2H), 4.99-4.68 (m, 2H), −113.52-−113.90 (m) 4.54 (d, J = 9.0 Hz, 0.5H), 4.24-4.14 (m, 0.5H), 3.77 (q, J = 6.8 Hz, 1H), 3.61-3.50 (m, 1H), 3.31 (d, J = 13.4 Hz, 3H), 3.15 (td, J = 8.9, 4.1 Hz, 1H), 3.02-2.88 (m, 2H), 2.73 (td, J = 7.5, 4.2 Hz, 2H), 2.47 (t, J = 12.5 Hz, 1H), 2.17-2.01 (m, 1H), 2.00-1.77 (m, 3H), 1.75-1.34 (m, 14H), 0.95-0.79 (m, 1H) F257 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 484.3 7.30-7.24 (m, 2H), 6.97-6.90 (m, 173.27, 158.83, ([M + Na]⁺) 1H), 6.90-6.85 (m, 2H), 154.90, 129.42, 5.05 (d, J = 8.2 Hz, 1H), 120.60, 114.44, 83.91, 4.95-4.79 (m, 1H), 4.28-4.09 (m, 79.84, 78.29, 75.17, 1H), 4.00 (td, J = 7.3, 6.4, 2.3 Hz, 66.15, 52.91, 40.31, 2H), 3.55-3.35 (m, 2H), 34.15, 30.28, 28.32, 3.10 (t, J = 8.9 Hz, 1H), 28.12, 18.95, 18.10, 2.31-2.10 (m, 2H), 1.87-1.75 (m, 11.07, 3.16, 2.92 1H), 1.75-1.58 (m, 3H), 1.50 (d, J = 11.8 Hz, 1H), 1.46-1.39 (m, 12H), 1.16 (q, J = 11.7 Hz, 1H), 1.11-0.95 (m, 2H), 0.54 (ddd, J = 8.0, 5.3, 3.8 Hz, 2H), 0.24-0.16 (m, 2H) F258 — — ESIMS ¹H NMR (CDCl₃) δ 5.16 (d, J = 7.5 Hz, ¹³C NMR (CDCl₃) δ m/z 336.2 1H), 4.95 (dq, J = 9.5, 174.15, 154.82, 86.81, ([M + Na]⁺) 6.2 Hz, 1H), 4.11 (ddd, J = 12.5, 79.86, 73.23, 67.71, 7.9, 5.2 Hz, 1H), 54.40, 39.68, 36.07, 3.80 (ddd, J = 8.6, 7.2, 3.6 Hz, 1H), 35.75, 33.00, 28.34, 3.68 (td, J = 9.0, 5.4 Hz, 1H), 21.72, 18.37 3.39 (dd, J = 9.5, 6.5 Hz, 1H), 2.31-2.18 (m, 1H), 2.05 (dddd, J = 11.8, 8.7, 5.4, 3.6 Hz, 1H), 1.98-1.79 (m, 2H), 1.75-1.64 (m, 1H), 1.64-1.55 (m, 1H), 1.53-1.46 (m, 2H), 1.44 (s, 9H), 1.40 (d, J = 6.3 Hz, 3H), 1.24 (ddd, J = 18.0, 11.7, 4.8 Hz, 1H) F259 — — — ¹H NMR (CDCl₃) δ 13 C NMR (CDCl₃) δ 7.34-7.19 (m, 2H), 7.02-6.86 (m, 173.35, 159.33, 3H), 5.76 (ddd, J = 17.2, 10.3, 138.51, 129.49, 8.0 Hz, 1H), 5.17-5.06 (m, 121.10, 116.18, 2H), 5.03 (d, J = 17.1 Hz, 1H), 115.78, 99.98, 80.46, 4.94 (d, J = 10.4 Hz, 1H), 74.39, 53.05, 47.47, 4.28 (t, J = 8.8 Hz, 1H), 34.13, 31.07, 28.34, 4.25-4.17 (m, 1H), 2.56-2.41 (m, 1H), 19.66, 18.36 2.27 (dt, J = 13.5, 6.6 Hz, 1H), 1.85 (td, J = 14.6, 7.1 Hz, 1H), 1.75 (dt, J = 14.8, 7.3 Hz, 1H), 1.65 (s, 1H), 1.44 (s, 9H), 1.33 (d, J = 6.4 Hz, 3H), 1.31-1.17 (m, 2H) F260 45-48 — ESIMS ¹H NMR (CDCl₃) δ 7.60 (d, J = 1.5 Hz, ¹⁹F NMR (CDCl₃) δ m/z 552 1H), 7.17 (d, J = 3.5 Hz, −112.78-−113.23 (m), ([M + H]⁺) 1H), 7.09-6.96 (m, 1H), −113.37-−113.71 (m) 6.77-6.63 (m, 2H), 6.52 (dd, J = 3.4, 1.7 Hz, 1H), 5.19 (q, J = 8.2, 7.2 Hz, 1H), 5.04 (dq, J = 12.5, 6.5 Hz, 1H), 4.90 (t, J = 8.7 Hz, 1H), 4.80 (d, J = 11.5 Hz, 1H), 4.58 (t, J = 9.0 Hz, 0.5H), 4.26 (t, J = 7.8 Hz, 0.5H), 3.32 (d, J = 12.2 Hz, 3H), 2.70 (dd, J = 13.9, 4.5 Hz, 1H), 2.52 (dd, J = 13.9, 10.1 Hz, 1H), 2.25-2.00 (m, 2H), 1.87-1.52 (m, 4H), 1.45 (s, 9H), 1.30 (d, J = 6.3 Hz, 3H), 1.13-0.96 (m, 1H) F261 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ m/z 536 7.22-7.05 (m, 1H), 6.84-6.71 (m, −113.49 (d, J = 43.3 Hz), ([M + H]⁺) 2H), 4.83 (dq, J = 34.5, 9.9 Hz, −113.74 (d, J = 31.5 Hz) 3H), 4.56 (d, J = 9.0 Hz, 0.5H), 4.20 (dd, J = 12.0, 6.7 Hz, 0.5H), 3.54 (t, J = 7.3 Hz, 1H), 3.47-3.37 (m, 0.5H), 3.37-3.25 (m, 3H), 3.20-3.09 (m, 1H), 3.03-2.85 (m, 2H), 2.71 (t, J = 7.6 Hz, 0.5H), 2.47 (td, J = 13.1, 12.3, 4.8 Hz, 1H), 2.17-1.99 (m, 1H), 1.99-1.76 (m, 1H), 1.74-1.32 (m, 16H), 1.04-0.77 (m, 7H) F262 161-163 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.62 (bs, ¹³C NMR (CDCl₃) δ 3394, (m/z) 3H), 7.26-7.08 (m, 2H), 170.45, 159.55, 2953, [M + H]⁺ 6.94-6.73 (m, 3H), 5.06-4.84 (m, 129.60, 121.07, 1747, calcd for 1H), 4.22-3.92 (m, 2H), 115.42, 81.29, 75.78, 1597, C₂₀H₃₂NO₃, 2.64-2.39 (m, 1H), 1.89-0.91 (m, 52.60, 43.19, 36.23, 1492, 334.2377; 13H), 0.90-0.59 (m, 7H) 31.23, 28.22, 27.80, 1225 found, 27.31, 23.01, 22.02, 334.2382 18.48, 18.33 F263 186-188 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.64 (bs, ¹³C NMR (CDCl₃) δ 3369, (m/z) 3H), 4.94-4.69 (m, 1H), 170.38, 84.06, 80.53, 2955, [M + H]⁺ 4.15-3.94 (m, 1H), 3.51-3.36 (m, 76.38, 52.45, 43.53, 1746, calcd for 1H), 3.31-3.17 (m, 1H), 36.38, 31.27, 29.16, 1642, C₁₈H₃₆NO₃, 3.03-2.88 (m, 1H), 2.64-2.39 (m, 28.03, 27.95, 27.23, 1475, 314.2690; 1H), 1.93-1.33 (m, 9H), 22.95, 22.23, 19.48, 1225 found, 1.41 (d, J = 6.2 Hz, 3H), 19.43, 18.34, 18.08 314.2690 1.33-0.98 (m, 3H), 0.98-0.77 (m, 12H) F264 205-207 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (bs, ¹³C NMR (CDCl₃) δ 3375, (m/z) 3H), 4.91-4.75 (m, 1H), 170.35, 84.09, 78.76, 2953, [M + H]⁺ 4.18-3.91 (m, 1H), 3.56-3.30 (m, 76.31, 52.42, 43.57, 1746, calcd for 2H), 3.05-2.91 (m, 1H), 43.54, 36.26, 31.27, 1634, C₁₈H₃₄NO₃, 2.61-2.38 (m, 1H), 1.85-1.32 (m, 27.98, 27.08, 23.00, 1454, 312.2533; 7H), 1.42 (d, J = 6.3 Hz, 3H), 22.16, 18.21, 18.01, 1233, found, 1.32-0.98 (m, 5H), 11.09, 3.08, 2.98 1076 312.2532 0.96-0.79 (m, 6H), 0.60-0.50 (m, 2H), 0.26-0.15 (m, 2H) F265 200-202 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.67 (bs, ¹³C NMR (CDCl₃) δ 3411, (m/z) 3H), 4.96-4.65 (m, 1H), 170.32, 84.33, 76.49, 2955, [M + H]⁺ 4.14-3.90 (m, 1H), 3.69-3.55 (m, 75.55, 52.41, 43.47, 2872, calcd for 1H), 3.51-3.37 (m, 1H), 36.37, 31.41, 28.04, 1748, C₁₇H₃₄NO₃, 3.04-2.89 (m, 1H), 2.61-2.41 (m, 27.28, 23.53, 23.01, 1478, 300.2533; 1H), 1.85-1.32 (m, 9H), 22.19, 18.32, 18.04, 1209 found, 1.43 (t, J = 8.5 Hz, 3H), 10.69 300.2532 1.30-0.98 (m, 4H), 0.93 (t, J = 7.4 Hz, 3H), 0.90-0.81 (m, 6H) F266 215-217 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.73 (bs, ¹³C NMR (CDCl₃) δ 3369, (m/z) 3H), 4.91-4.77 (m, 1H), 170.41, 127.08 (q, J = 277 Hz), 1744, [M + H]⁺ 4.03-3.89 (m, 1H), 3.81-3.63 (m, 84.51, 76.13, 1635, calcd for 1H), 3.61-3.48 (m, 1H), 71.66, 52.43, 43.44, 1453, C₁₈H₃₃F₃NO₃, 3.04-2.94 (m, 1H), 2.59-2.45 (m, 36.32, 31.17, 30.72 (q, 1252 368.2407; 1H), 2.29-2.08 (m, 2H), J = 31 Hz), 28.09, found, 1.87-1.43 (m, 9H), 1.40 (d, J = 6.4 Hz, 27.98, 27.17, 23.01 (q, 368.2418 3H), 1.31-0.90 (m, 4H), J = 3.2 Hz), 22.89, 0.90-0.83 (m, 6H) 22.08, 18.30, 18.01 ¹⁹F NMR (CDCl₃) δ −66.49 F267 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.69 (bs, — 2952, (m/z) 3H), 4.88-4.73 (m, 1H), 1746, [M + H]⁺ 4.11-3.89 (m, 2H), 3.17-2.98 (m, 1453, calcd for 1H), 2.96-2.46 (m, 2H), 1208, C₁₉H₃₆NO₃, 1.89-0.96 (m, 21H), 1054 326.2690; 0.95-0.81 (m, 6H) found, 326.2687 F268 218-220 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.70 (bs, — 2932, (m/z) 3H), 4.91-4.71 (m, 1H) 2874, [M + H]⁺ 4.12-3.91 (m, 1H), 3.49 (s, 3H), 1751, calcd for 2.98-2.83 (m, 1H), 1580, C₁₅H₃₀NO₃, 2.61-2.40 (m, 1H), 1.88-1.35 (m, 1481, 272.2220; 7H), 1.43 (d, J = 6.4 Hz, 3H), 1211 found, 1.30-1.02 (m, 4H), 272.2222 0.95-0.80 (m, 6H) F269 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.70 (bs, ¹³C NMR (CDCl₃) δ 3404, (m/z) 3H), 5.09-4.90 (m, 1H), 176.09, 170.16, 75.71, 2952, [M + H]⁺ 4.90-4.76 (m, 1H), 4.15-3.95 (m, 74.41, 52.33, 44.02, 1732, calcd for 1H), 2.84-2.65 (m, 2H), 43.59, 41.80, 36.15, 1453, C₂₀H₃₆NO₄, 2.64-2.47 (m, 1H), 2.01-1.36 (m, 30.04, 29.94, 29.92, 1383, 354.2639; 14H), 1.35-0.91 (m, 7H), 27.90, 25.80, 25.67, 1149 found, 0.91-0.76 (m, 6H) 25.66, 22.84, 22.13, 354.2655 18.20, 17.43 F271 222-224 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (bs, ¹⁹F NMR (CDCl₃) δ −117.24 2923, (m/z) 3H), 7.14-7.03 (m, 2H), 2877, [M + H]⁺ 7.01-6.89 (m, 2H), 4.91-4.72 (m, 1746, calcd for 1H), 4.11-3.89 (m 1H), 1508, C₂₀H₂₉FNO₃, 3.58-3.48 (m, 1H), 3.46-3.35 (m, 1218, 350.2126; 1H), 3.16-2.96 (m, 2H), 1073 found, 2.51-2.34 (m, 1H), 2.34-2.18 (m, 350.2130 1H) 1.86-1.68 (m, 1H), 1.66-1.24 (m, 4H), 1.39 (d, J = 6.5 Hz, 3H), 1.18-1.01 (m, 1H), 0.84-0.68 (m, 1H), 0.65-0.51 (m, 2H), 0.30-0.17 (m, 2H) F272 196-198 — HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (bs, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.34-7.25 (m, 2H), 170.26, 161.32 (d, J = 244.1 Hz), [M + H]⁺ 7.06-6.86 (m, 7H), 5.09-4.92 (m, 159.34, calcd for 1H), 4.32-4.18 (m, 1H), 135.46 (d, J = 3.2 Hz), C₂₂H₂₇FNO₃, 4.16-3.97 (m, 1H), 2.97-2.85 (m, 130.03 (d, J = 7.9 Hz), 372.1969; 1H), 2.59-2.41 (m, 1H), 129.79, 121.46, found, 2.34-2.21 (m, 1H), 2.07-1.91 (m, 115.38, 115.18 (d, J = 20.9 Hz), 372.1979 1H), 1.76-1.37 (m, 4H), 80.66, 75.74, 1.27 (d, J = 6.4 Hz, 3H), 52.43, 45.39, 36.01, 1.00-0.81 (m, 1H) 31.13, 26.78, 18.38, 18.21 ¹⁹F NMR (CDCl₃) δ −117.02 F273 210-212 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.56 (bs, ¹³C NMR (75 MHz, 3378, (m/z) 3H), 7.15-7.01 (m, 2H), CDCl₃) δ 170.33, 2937, [M + H]⁺ 7.01-6.86 (m, 2H), 6.03-5.83 (m, 161.39 (d, J = 244.0 Hz), 1743, calcd for 1H), 5.33 (d,J = 17.2 Hz, 1H), 136.02 (d, J = 3.1 Hz), 1601, C₁₉H₂₇FNO₃, 5.22 (d, J = 10.4 Hz, 1H), 134.25, 1508, 336.1969; 4.92-4.74 (m, 1H), 4.25 (dd, J = 12.1, 130.16 (d, J = 7.5 Hz), 1218 found, 5.5 Hz, 1H), 117.36, 115.25 (d, J = 21.1 Hz), 336.1970 4.16-3.88 (m, 2H), 3.82-3.58 (m, 1H), 83.99, 76.11, 3.24-3.09 (m, 1H), 74.89, 52.40, 45.75, 3.09-2.93 (m, 1H), 2.55-2.35 (m, 36.12, 31.17, 26.73, 1H), 2.35-2.16 (m, 1H), 18.38, 18.09 1.87-1.70 (m, 1H), 1.70-1.28 (m, 6H), 0.89-0.67 (m, 1H) F274 215-217 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.64 (bs, — 3385, (m/z) 3H), 7.22-6.74 (m, 4H), 2934, [M + H]⁺ 4.99-4.66 (m, 1H), 4.05-3.57 (m, 2876, calcd for 3H), 3.57-3.39 (m, 1H), 1742, C₁₉H₂₉FNO₃, 3.16-2.92 (m, 2H), 2.85-2.67 (m, 1508, 338.2126; 1H), 2.57-2.36 (m, 1H), 1215 found, 2.36-2.16 (m, 1H), 1.86-1.25 (m, 338.2126 8H), 0.97 (t, J = 7.4 Hz, 3H), 0.89-0.63 (m, 1H) F275 163-165 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.60 (bs, — 2956, (m/z) 3H), 7.24-6.79 (m, 4H), 2875, [M + H]⁺ 5.04-4.67 (m, 2H), 4.12-3.84 (m, 1748, calcd for 1H), 3.59-3.46 (m, 1H), 1509, C₂₀H₃₁FNO₃, 3.38-3.21 (m, 1H), 3.18-2.93 (m, 1221 352.2282; 2H), 2.56-2.36 (m, 1H), found, 2.36-2.17 (m, 1H), 1.99-1.80 (m, 352.2282 1H), 1.80-1.29 (m, 7H), 1.05-0.67 (m, 7H) F276 204-206 (Neat) HRMS-ESI ¹H NMR (CD₃OD) δ ¹⁹F NMR (CDCl₃) δ −113.38, 2942, (m/z) 7.27-7.16 (m, 2H), 7.08-6.96 (m, −121.92 (2F) 2882, [M + H]⁺ 2H), 5.99 (tt, J = 55.1, 3.7 Hz, 1740, calcd for 1H), 5.02-4.92 (m, 1H), 1509, C₁₈H₂₅F₃NO₃, 4.09-3.81 (m, 3H), 3.79-3.57 (m, 1216 360.1781; 1H), 3.45-3.38 (m, 1H), found, 3.17-3.06 (m, 1H), 2.45 (dd, J = 13.5, 360.1786 11.5 Hz, 1H), 2.29-2.14 (m, 1H), 1.92-1.75 (m, 1H), 1.75-1.57 (m, 2H), 1.52 (d, J = 6.4 Hz, 3H), 1.41-1.27 (m, 1H), 0.99-0.81 (m, 1H) F277 200-202 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (bs, ¹⁹F NMR (CDCl₃) δ −116.96 3376, (m/z) 3H), 7.09-7.00 (m, 2H), 2954, [M + H]⁺ 7.00-6.89 (m, 2H), 5.06-4.87 (m, 1733, calcd for 2H), 4.14-3.93 (m, 1H), 1635, C₂₂H₃₁FNO₄, 2.81-2.57 (m, 2H), 2.57-2.40 (m, 1509, 392.2232; 1H), 2.40-2.25 (m, 1H), 1220 found, 2.03-1.41 (m, 11H), 392.2236 1.38-1.14 (m, 5H), 0.99-0.78 (m, 1H) F278 193-195 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (bs, ¹³C NMR (CDCl₃) δ 3375, (m/z) 3H), 7.08-6.99 (m, 2H), 176.43, 170.09, 2972, [M + H]⁺ 6.99-6.90 (m, 2H), 5.10-4.82 (m, 161.39 (d, J = 244.2 Hz), 1735, calcd for 2H), 4.12-3.91 (m, 1H), 135.23 (d, J = 3.2 Hz), 1635, C₂₀H₂₉FNO₄, 2.69-2.38 (m, 3H) 2.31 (dd J = 13.8, 130.02 (d, J = 7.7 Hz), 1509, 366.2075; 11.1 Hz, 1H), 115.27 (d, J = 21.3 Hz), 1219 found, 1.99-1.80 (m, 1H), 1.76-1.40 (m, 3H), 75.11, 74.26, 366.2077 1.33-1.12 (m, 10H), 52.24, 43.84, 35.77, 0.97-0.78 (m, 1H) 34.17, 33.62, 26.65, 19.07, 18.97, 18.82, 17.36 ¹⁹F NMR (CDCl₃) δ −116.88 F279 — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) δ m/z 334.4 7.31-7.22 (m, 2H), 7.21-7.13 (m, 171.46, 141.99, ([M + H]⁺) 3H), 3.98-3.83 (m, 1H), 129.89, 129.46, 3.77-3.70 (m, 1H), 3.66 (q, J = 5.5, 127.06, 84.74, 81.69, 5.0 Hz, 1H), 77.66, 53.00, 47.35, 3.61-3.53 (m, 1H), 3.41 (dd, J = 8.5, 6.4 Hz, 37.69, 32.11, 30.51, 1H), 3.23 (t, J = 8.9 Hz, 28.03, 19.88, 19.83, 1H), 3.10 (dd, J = 13.3, 3.4 Hz, 19.45, 18.49 1H), 2.47-2.30 (m, 1H), 2.20 (qd, J = 8.4, 7.5, 5.0 Hz, 1H), 1.89 (dt, J = 13.2, 6.6 Hz, 1H), 1.84-1.74 (m, 1H), 1.64 (dp, J = 8.5, 3.2, 2.8 Hz, 2H), 1.48 (d, J = 6.4 Hz, 4H), 1.36-1.24 (m, 2H), 0.98 (dd, J = 6.7, 3.6 Hz, 6H), 0.95-0.79 (m, 2H) F280 — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CDCl₃) δ m/z 333.4 7.33-7.22 (m, 2H), 7.22-7.11 (m, 173.98, 144.51, ([M + H]⁺) 3H), 3.91 (dd, J = 10.9, 7.1 Hz, 132.44, 131.98, 1H), 3.66-3.59 (m, 2H), 129.58, 87.29, 82.26, 3.51 (dd, J = 9.9, 6.8 Hz, 1H), 80.13, 70.67, 55.51, 3.30-3.23 (m, 2H), 3.15 (dd, 49.75, 40.33, 34.61, J = 13.1, 3.3 Hz, 1H), 30.63, 21.94, 20.95, 2.39 (dd, J = 13.3, 11.6 Hz, 1H), 14.60, 6.06 2.20 (ddt, J = 12.6, 8.6, 4.6 Hz, 1H), 1.80 (ddt, J = 12.0, 7.9, 4.0 Hz, 1H), 1.63 (dq, J = 9.5, 5.3, 4.4 Hz, 2H), 1.56-1.40 (m, 4H), 1.40-1.25 (m, 1H), 1.12 (dddd, J = 14.9, 6.9, 5.9, 2.7 Hz, 1H), 0.94-0.77 (m, 1H), 0.64-0.47 (m, 2H), 0.32-0.17 (m, 2H) F281 — — ESIMS ¹H NMR (CDCl₃) δ 8.66 (s, — m/z 354.3 3H), 7.35-7.27 (m, 2H), ([M + H]⁺) 7.25-7.11 (m, 3H), 7.07 (d, J = 7.3 Hz, 2H), 7.03-6.93 (m, 3H), 5.04 (s, 1H), 4.47-4.34 (m, 1H), 4.29 (s, 1H), 3.77 (dddd, J = 5.9, 4.6, 2.8, 1.8 Hz, 1H), 3.68-3.60 (m, 1H), 2.97 (d, J = 12.2 Hz, 1H), 2.31 (t, J = 12.3 Hz, 1H), 2.07 (s, 1H), 1.92-1.77 (m, 2H), 1.73-1.36 (m, 4H), 0.96-0.83 (m, 1H) F282 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.29-7.23 (m, 2H), 170.16, 140.43, [M + H]⁺ 7.20-7.09 (m, 3H), 4.88-4.76 (m, 128.76, 128.37, calcd for 1H), 4.03-3.91 (m, 1H), 125.96, 83.70, 76.33, C₁₉H₃₀NO₃, 3.55-3.43 (m, 1H), 3.16-2.98 (m, 75.68, 52.19, 45.95, 320.222; 2H), 2.49-2.38 (m, 1H), 36.74, 31.33, 26.28, found, 2.29 (dd, J = 13.2, 11.8 Hz, 1H), 23.58, 18.18, 17.97, 320.2218 1.87-1.73 (m, 1H), 10.74 1.70-1.50 (m, 5H), 1.50-1.36 (m, 2H), 1.41 (d, J = 6.5 Hz, 3H), 0.97 (t, J = 7.4 Hz, 3H), 0.79-0.69 (m, 1H) F283 — — ESIMS ¹H NMR (CDCl₃) δ 8.57 (s, — m/z 347.4 3H), 7.36-7.20 (m, 2H), ([M + H]⁺) 7.20-7.05 (m, 3H), 4.94-4.66 (m, 1H), 4.22-3.89 (m, 2H), 3.37-3.07 (m, 2H), 2.87 (t, J = 7.6 Hz, 1H), 2.70 (dd,J = 8.2, 7.0 Hz, 1H), 2.54-2.33 (m, 1H), 2.33-2.11 (m, 1H), 1.87-1.64 (m, 7H), 1.43 (br s, 4H), 1.26 (br s, 3H), 0.93-0.70 (m, 1H) F284 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.29-7.22 (m, 2H), 170.22, 140.40, [M + H]⁺ 7.20-7.10 (m, 3H), 4.81 (dq, J = 9.4, 128.77, 128.37, calcd for 6.4 Hz, 1H), 125.96, 83.92, 76.21, C₁₈H₂₈NO₃, 4.05-3.91 (m, 1H), 3.78 (dq, J = 8.8, 6.9 Hz, 69.30, 55.22, 45.84, 306.2064; 1H), 3.59 (dq, J = 8.9, 7.0 Hz, 36.83, 31.26, 26.29, found, 1H), 3.15-3.07 (m, 1H) 18.15, 17.89, 15.72 306.2062 3.07-3.00 (m, 1H), 2.47-2.37 (m, 1H), 2.35-2.24 (m, 1H), 1.84-1.71 (m, 1H), 1.61-1.48 (m, 2H), 1.47-1.35 (m, 2H), 1.40 (d, J = 6.5 Hz, 3H), 1.24 (t, J = 6.9 Hz, 3H), 0.79-0.65 (m, 1H) F285 — — ESIMS 1H NMR (300 MHz, CD₃OD) 13C NMR (75 MHz, m/z 336.2 δ 7.35-7.22 (m, 2H), 7.17 (d, CD3OD) δ 170.26, ([M + H]⁺) J = 7.4 Hz, 3H), 4.84 (d, J = 1.0 Hz, 140.88, 128.80, 1H), 3.92 (dt, J = 10.0, 128.26, 125.84, 84.19, 4.8 Hz, 2H), 3.74 (dq, J = 10.8, 76.24, 72.70, 72.14, 5.5, 5.0 Hz, 1H), 3.65 (s, 66.97, 58.07, 51.86, 3H), 3.55 (t, J = 4.3 Hz, 2H), 45.94, 36.51, 30.93, 3.37 (s, 3H), 3.34-3.25 (m, 26.79, 18.27, 17.31 1H), 3.16 (dd, J = 13.2, 3.3 Hz, 1H), 2.38 (t, J = 12.4 Hz, 1H), 2.31-2.17 (m, 1H), 1.88-1.73 (m, 1H), 1.72-1.56 (m, 2H), 1.49 (d, J = 6.3 Hz, 4H), 1.39-1.24 (m, 1H), 0.91-0.76 (m, 1H) F287 — — HRMS-ESI ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) δ (m/z) 7.33 (ddd, J = 9.8, 5.9, 2.2 Hz, 2H), 170.13, 159.60, ([M]⁺) 7.14-7.03 (m, 4H), 6.98 (t, J = 7.3 Hz, 158.13, 131.91, calcd for 1H), 6.83 (d, J = 8.6 Hz, 129.39, 129.32, C₂₃H₂₉NO₄, 2H), 5.14 (dq, J = 9.7, 6.4 Hz, 120.97, 115.15, 383.2097; 1H), 4.47 (t, J = 8.9 Hz, 113.45, 80.41, 75.60, found, 1H), 3.98 (dd, J = 10.9, 7.1 Hz, 54.21, 51.63, 45.69, 383.2075 1H), 3.76 (s, 3H), 35.49, 30.78, 26.56, 2.92 (dd, J = 13.5, 3.4 Hz, 1H), 18.02, 17.21 2.37 (dd, J = 13.4, 11.6 Hz, 1H), 2.26 (ddd, J = 11.9, 7.4, 4.2 Hz, 1H), 2.03 (ddd, J = 10.5, 7.3, 3.6 Hz, 1H), 1.75 (d, J = 9.3 Hz, 2H), 1.62 (tt, J = 13.4, 6.6 Hz, 1H), 1.37 (d, J = 6.4 Hz, 4H), 1.01 (d, J = 14.8 Hz, 1H) F288 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.76 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.31-7.22 (m, 2H), 170.30, 159.58, ([M]⁺) 6.99-6.84 (m, 3H), 5.03 (p, J = 6.6 Hz, 129.62, 121.09, calcd for 1H), 4.26-3.96 (m, 2H), 115.49, 81.25, 76.00, C₂₁H₃₁NO₃, 3.71 (s, 3H), 2.64-2.51 (m, 67.09, 52.45, 42.05, 345.2304; 1H), 2.04-1.59 (m, 6H), 37.15, 36.76, 33.63, found, 1.59-1.31 (m, 5H), 1.28 (d, J = 6.3 Hz, 31.73, 31.41, 27.29, 345.2287 3H), 1.08-0.88 (m, 3H) 25.04, 18.51, 18.32 F289 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.67 (s, — Film) (m/z) 3H), 6.99 (d, J = 8.2 Hz, 2H), 2946, ([M]⁺) 6.80 (d, J = 7.9 Hz, 2H), 2871, calcd for 4.97 (s, 1H), 3.78 (s, 3H), 2.73 (p, J = 7.8 Hz, 1733, C₂₃H₃₃NO₅, 1H), 2.59 (d, J = 12.9 Hz, 1512, 403.2359; 1H), 2.49 (s, 1H), 1246, found, 2.28 (t, J = 12.3 Hz, 1H), 1177 403.2347 1.98-1.70 (m, 10H), 1.65-1.57 (m, 4H), 1.30-1.24 (m, 3H), 1.15 (s, 1H), 0.87 (s, 1H) F290 — — ESIMS ¹H NMR (CDCl₃) δ 8.64 (s, ¹⁹F NMR (CDCl₃) δ m/z 400 3H), 7.03 (d, J = 8.3 Hz, 2H), −89.67-−89.77 (m) ([M + H]⁺) 6.81 (d, J = 8.4 Hz, 2H), 4.89-4.79 (m, 1H), 3.99-3.85 (m, 2H), 3.78 (s, 3H), 3.11 (t, J = 9.0 Hz, 1H), 2.96 (d, J = 12.7 Hz, 1H), 2.51-2.36 (m, 1H), 2.33-2.09 (m, 3H), 1.75 (s, 1H), 1.73-1.58 (m, 6H), 1.46-1.39 (m, 4H), 0.81-0.72 (m, 1H) F291 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ (m/z) 8.82-8.25 (br s, 3H), 7.12-6.95 (m, 170.10, 157.88, ([M]⁺) 2H), 6.87-6.76 (m, 2H), 132.29, 129.64, calcd for 4.85 (dd, J = 9.1, 6.2 Hz, 1H), 113.85, 83.49, 78.87, C₂₁H₃₁NO₄, 3.98-3.89 (m, 1H), 3.78 (s, 3H), 76.43, 55.26, 52.16, 361.2253; 3.55 (dd, J = 9.7, 7.0 Hz, 1H), 46.07, 35.85, 31.47, found, 3.42 (dd, J = 9.7, 6.8 Hz, 1H), 26.25, 18.13, 17.98, 361.2245 3.19-2.97 (m, 2H), 11.15, 3.18, 3.01 2.51-2.37 (m, 1H), 2.24 (t, J = 12.5 Hz, 1H), 1.87-1.73 (m, 2H), 1.59-1.38 (m, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.11 (td, J = 7.4, 3.8 Hz, 1H), 0.79-0.68 (m, 1H), 0.62-0.43 (m, 2H), 0.24 (dq, J = 7.3, 4.5, 3.1 Hz, 2H) F292 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ — Film) (m/z) 8.79-8.60 (br s, 3H), 4.96-4.71 (m, 3411, ([M]⁺) 1H), 4.10-3.73 (m, 1H), 2943, calcd for 3.48 (dd, J = 9.6, 7.0 Hz, 1H), 2869, C₁₉H₃₃NO₃, 3.34 (dd, J = 9.6, 6.9 Hz, 1H), 1746, 323.2460; 2.95 (t, J = 8.9 Hz, 1H), 1233, found, 2.68-2.43 (m, 1H), 1.87-1.48 (m, 12H), 1070 323.2471 1.49-1.29 (m, 2H), 1.42 (d, J = 6.3 Hz, 3H), 1.07 (dt, J = 12.6, 6.8 Hz, 3H), 0.97-0.81 (m, 1H), 0.59-0.48 (m, 2H), 0.25-0.16 (m, 2H) F293 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.61 (br s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.03 (d, J = 8.3 Hz, 2H), 170.15, 157.86, ([M]⁺) 6.87-6.68 (m, 2H), 4.85 (td, J = 27.2, 132.41, 129.62, calcd for 23.8, 14.0 Hz, 1H), 113.87, 113.84, 83.42, C₂₁H₃₃NO₄, 3.96 (s, 1H), 3.78 (s, 3H), 83.33, 80.77, 55.26, 363.2410; 3.56-3.47 (m, 1H), 3.31 (t, J = 7.6 Hz, 46.21, 35.67, 29.25, found, 1H), 3.08 (t, J = 9.0 Hz, 19.52, 19.47, 18.23, 363.2396 1H), 3.03-2.95 (m, 1H), 18.15, 18.07 2.76 (br s, 1H), 2.55-2.37 (br s, 1H), 2.23 (t, J = 12.5 Hz, 1H), 2.14-1.99 (m, 1H), 1.88 (dt, J = 13.1, 6.6 Hz, 1H), 1.67-1.34 (m, 6H), 0.96 (dd, J = 6.7, 5.2 Hz, 6H), 0.76 (s, 1H) F294 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.61 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.03 (d, J = 8.5 Hz, 2H), 170.13, 157.86, ([M]⁺) 6.88-6.66 (m, 2H), 132.36, 129.63, calcd for 4.93-4.75 (m, 1H), 3.96 (d, J = 8.1 Hz, 113.82, 83.68, 75.71, C₂₀H₃₁NO₄, 1H), 3.78 (s, 3H), 3.49 (dt, 67.09, 55.25, 52.16, 349.2253; J = 8.7, 6.7 Hz, 1H), 3.09 (t, J = 9.1 Hz, 46.08, 35.78, 31.44, found, 1H), 3.00 (d, J = 10.9 Hz, 26.23, 23.57, 18.16, 349.2234 1H), 2.44 (dd, J = 13.3, 17.97, 10.73 6.6 Hz, 1H), 2.24 (t, J = 12.5 Hz, 1H), 1.77 (d, J = 23.7 Hz, 3H), 1.68-1.51 (m, 3H), 1.43 (t, J = 7.1 Hz, 5H), 0.97 (t, J = 7.4 Hz, 3H), 0.74 (d, J = 14.8 Hz, 1H) F295 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 3H), 7.29 (d, J = 1.7 Hz, 1H), 170.21, 154.29, 2956, ([M]⁺) 6.26 (dd, J = 3.1, 1.8 Hz, 1H), 141.09, 110.13, 2876, calcd for 5.99 (d, J = 3.0 Hz, 1H), 106.15, 83.19, 80.39, 1746, C₁₈H₂₉NO₄, 4.89-4.82 (m, 1H), 3.98 (s, 1H), 76.34, 69.65, 52.33, 1536, 323.2097; 3.47 (t, J = 7.5 Hz, 1H), 43.11, 31.32, 29.28, 1231, found, 3.28 (t, J = 7.4 Hz, 1H), 3.10 (td, J = 8.9, 29.19, 27.72, 19.47, 1207 323.2107 4.7 Hz, 1H), 19.44, 18.08 3.01-2.92 (m, 1H), 2.53-2.37 (m, 2H), 2.05 (s, 1H), 1.88 (dp, J = 19.7, 7.9, 6.9 Hz, 2H), 1.60 (d, J = 18.9 Hz, 4H), 1.49-1.36 (m, 3H), 0.93 (d, J = 6.6 Hz, 6H) F296 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.70 (s, — Film) (m/z) 3H), 5.01-4.92 (m, 1H), 3392, ([M]⁺) 4.86-4.74 (m, 1H), 4.05 (s, 1H), 2943, calcd for 3.76-3.66 (m, 1H), 2871, C₁₉H₃₃NO₄, 2.63-2.49 (m, 1H), 1.81-0.83 (m, 1736, 339.2410; 26H) 1455, found, 1187, 339.2409 1153, 1063 F297 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.71 (s, — Film) (m/z) 1H), 4.92-4.78 (m, 1H), 3390, ([M]⁺) 3.69-3.57 (m, 1H), 3.47-3.37 (m, 2942, calcd for 1H), 2.95 (t, J = 8.9 Hz, 1H), 2869, C₁₈H₃₃NO₃, 2.86-2.79 (m, 1H), 1744, 311.2460; 2.57-2.50 (m, 1H), 1.86-1.31 (m, 1453, found, 19H), 1.15-0.96 (m, 4H), 1230, 311.2466 0.93 (t, J = 7.3 Hz, 3H) 1095, 729 F298 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.68 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 4.89-4.75 (m, 1H), 170.29, 128.37, 83.94, ([M]⁺) 3.99 (s, 1H), 3.84-3.61 (m, 3H), 80.52, 42.30, 37.10, calcd for 3.50-3.41 (m, 1H), 37.06, 36.60, 33.91, C₁₉H₃₅NO₃, 3.27-3.18 (m, 2H), 2.93 (t, J = 8.8 Hz, 31.65, 29.16, 25.09, 325.2617; 1H), 2.85-2.79 (m, 1H), 25.05, 19.48, 19.37, found, 2.52 (s, 1H), 1.91-1.71 (m, 18.43, 18.28, 18.11, 325.2619 3H), 1.65-1.47 (m, 5H), 18.06 1.15-0.85 (m, 14H) F299 — — ESIMS — — m/z 278.2 ([M + H]⁺) F300 — — ESIMS — — m/z 292.2 ([M + H]⁺) F301 — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) δ m/z 334.4 7.31-7.22 (m, 2H), 7.21-7.13 (m, 171.46, 141.99, ([M + H]⁺) 3H), 3.98-3.83 (m, 1H), 129.89, 129.46, 3.77-3.70 (m, 1H), 3.66 (q, J = 5.5, 127.06, 84.74, 81.69, 5.0 Hz, 1H), 77.66, 53.00, 47.35, 3.61-3.53 (m, 1H), 3.41 (dd, J = 8.5, 6.4 Hz, 37.69, 32.11, 30.51, 1H), 3.23 (t, J = 8.9 Hz, 28.03, 19.88, 19.83, 1H), 3.10 (dd, J = 13.3, 3.4 Hz, 19.45, 18.49 1H), 2.47-2.30 (m, 1H), 2.20 (qd, J = 8.4, 7.5, 5.0 Hz, 1H), 1.89 (dt, J = 13.2, 6.6 Hz, 1H), 1.84-1.74 (m, 1H), 1.64 (dp, J = 8.5, 3.2, 2.8 Hz, 2H), 1.48 (d, J = 6.4 Hz, 4H), 1.36-1.24 (m, 2H), 0.98 (dd, J = 6.7, 3.6 Hz, 6H), 0.95-0.79 (m, 2H) F302 — — ESIMS ¹H NMR (CDCl₃) δ 8.54 (s, ¹³C NMR (CDCl₃) δ m/z 348 3H), 7.18-6.88 (m, 4H), 170.32, 137.33, ([M + H]⁺) 4.83 (s, 1H), 4.30-3.82 (m, 1H), 135.36, 129.08, 3.62-3.43 (m, 1H), 128.67, 83.50, 80.81, 3.43-3.21 (m, 1H), 3.23-2.90 (m, 76.36, 52.63, 46.21, 2H), 2.31 (s, 5H), 1.83 (d, J = 41.6 Hz, 36.20, 31.43, 29.28, 2H), 1.68-1.15 (m, 26.16, 21.04, 19.58, 7H), 0.96 (t, J = 5.9 Hz, 6H), 19.52, 18.35, 18.22 0.81-0.60 (m, 1H) F303 — — ESIMS ¹H NMR (DMSO-d₆) δ 8.40 (s, ¹³C NMR (DMSO-d₆) m/z 290.2 3H), 4.91-4.71 (m, 1H), δ 170.43, 83.07, 82.65, ([M + H]⁺) 4.56 (d, J = 4.7 Hz, 1H), 4.43 (t, J = 6.0 Hz, 81.46, 78.94, 75.34, 1H), 3.88 (dd, J = 10.4, 51.12, 30.33, 28.51, 6.9 Hz, 1H), 3.42 (dd, J = 8.6, 27.71, 19.14, 19.11, 6.6 Hz, 1H), 3.26 (dd, J = 8.6, 17.96, 17.75 6.4 Hz, 1H), 3.09 (t, J = 8.6 Hz, 1H), 2.13 (dd, J = 13.2, 6.5 Hz, 1H), 2.05-1.85 (m, 1H), 1.86-1.48 (m, 5H), 1.45-1.27 (m, 5H), 0.87 (d, J = 6.7 Hz, 6H) F304 210 — ESIMS ¹H NMR (CD₃OD) δ 7.08 (s, ¹³C NMR (CD₃OD) δ (dec) m/z 346 4H), 4.87 (s, 1H), 171.19, 138.52, ([M + H]⁺) 4.13-3.42 (m, 3H), 3.30 (d, J = 19.1 Hz, 136.24, 129.92, 1H), 3.08 (s, 1H), 2.29 (s, 5H), 129.76, 84.73, 79.80, 1.57 (q, J = 58.8, 55.9 Hz, 77.27, 53.39, 47.04, 8H), 1.13 (s, 1H), 0.85 (d, J = 11.7 Hz, 37.36, 32.14, 27.85, 1H), 0.56 (s, 2H), 21.08, 19.65, 18.63, 0.27 (s, 2H) 11.98, 3.64, 3.63 F305 — — ESIMS — — m/z 384.9 ([M + H]⁺) F306 — — ESIMS — — m/z 321.9 ([M + H]⁺) F307 — — ESIMS — — m/z 318.5 ([M + H]⁺) F308 200-210 ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) d (dec) m/z 368 7.44-6.80 (m, 9H), 5.14 (s, 1H), 171.05, 160.65, ([M + H]⁺) 4.46 (s, 1H), 3.63 (s, 4H), 137.89, 136.19, 2.86 (s, 1H), 2.60-1.14 (m, 12H), 130.75, 129.87, 0.96 (s, 1H) 129.75, 122.14, 117.03, 81.89, 76.55, 68.05, 46.67, 37.46, 32.38, 27.71, 21.05, 20.12, 18.85 F309 — — ESIMS — — (m/z) 302.3 ([M + H]⁺) F310 — — ESIMS — — (m/z) 272.2 ([M + H]⁺) F311 233-237 — ESIMS 1H NMR (CD₃OD) δ ¹³C NMR (101 MHz, m/z 404 7.44-7.25 (m, 5H), 7.24-7.15 (m, CD₃OD) δ 171.39, ([M + H]⁺) 1H), 6.92-6.82 (m, 2H), 162.92 (dd, J = 245.6, 4.96 (dq, J = 9.4, 6.5 Hz, 1H), 12.2 Hz), 162.52 (dd, J = 246.5, 4.81 (d, J = 11.1 Hz, 1H), 4.66 (d, J = 11.2 Hz, 12.1 Hz), 1H), 3.96 (dd, J = 10.9, 139.36, 133.26 (dd, J = 9.5, 7.1 Hz, 1H), 3.49 (t, J = 8.9 Hz, 6.7 Hz), 129.44, 1H), 3.04 (dd, J = 13.7, 128.93, 128.88, 3.5 Hz, 1H), 2.51 (dd, J = 13.6, 124.57 (dd, J = 15.9, 11.4 Hz, 1H), 3.9 Hz), 112.10 (dd, J = 20.9, 2.34-2.20 (m, 1H), 1.88 (ddq, J = 12.1, 3.9 Hz), 8.0, 3.9 Hz, 1H), 105.04-103.87 (m), 84.75, 1.74-1.60 (m, 2H), 1.53 (d, J = 6.4 Hz, 77.35, 76.41, 52.98, 3H), 1.50-1.40 (m, 1H), 45.56, 32.02, 30.42, 1.35 (dtd, J = 13.3, 10.4, 3.2 Hz, 28.52, 19.46, 18.50 1H), 0.92 (ddt, J = 14.7, ¹⁹F NMR (CD₃OD) δ 6.7, 3.4 Hz, 1H) 61.08 (d, J = 6.4 Hz), 60.97 (d, J = 6.5 Hz) F312 — — ESIMS — — (m/z) 370.1 ([M + H]⁺) F313 — — ESIMS — — (m/z) 292.2 ([M + H]+) F314 — — ESIMS — — (m/z) 328.5 ([M + H]⁺) F315 — — ESIMS — — (m/z) 340.3 ([M + H]⁺) F316 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ m/z 402 7.31-7.23 (m, 1H), 7.21-7.12 (m, −66.34 (d, J = 3.6 Hz) ([M + H]⁺) 2H), 7.08 (d, J = 7.7 Hz, 2H), 6.99 (d, J = 7.8 Hz, 2H), 4.98-4.73 (m, 1H), 3.84-3.72 (m, 1H), 3.57 (q, J = 6.9 Hz, 1H), 3.11 (dt, J = 8.5, 5.5 Hz, 1H), 2.92 (d, J = 13.4 Hz, 1H), 2.75 (s, 1H), 2.58-2.39 (m, 1H), 2.38-2.09 (m, 5H), 1.83 (tt, J = 15.7, 7.5 Hz, 3H), 1.72-1.31 (m, 5H), 0.87-0.64 (m, 1H) F317 190-195 — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ (dec) m/z 432 7.34-7.14 (m, 5H), 7.08 (q, J = 7.9 Hz, −113.07 (dd, J = 44.4, ([M + H]⁺) 1H), 6.87-6.71 (m, 2H), 6.6 Hz), −113.76 (dd, J = 21.5, 4.98-4.77 (m, 1H), 6.6 Hz) 3.83-3.71 (m, 1H), 3.61-3.48 (m, 1H), 3.21-3.07 (m, 1H), 3.02-2.88 (m, 1H), 2.73 (dp, J = 12.2, 3.9 Hz, 3H), 2.57-2.35 (m, 2H), 2.08-1.30 (m, 10H), 0.83 (p, J = 11.1, 8.5 Hz, 1H) F318 — — ESIMS — — m/z 362.3 ([M + H]⁺) F319 — — ESIMS — — m/z 214.2 ([M + H]⁺) F320 — — ESIMS — — m/z 290.2 ([M + H]⁺) F321 67-73 — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) δ m/z 370 7.19-7.10 (m, 1H), 6.98-6.81 (m, 171.35, 162.87 (dd, J = 245.7, ([M + H]⁺) 2H), 3.94 (dd, J = 10.8, 7.3 Hz, 12.4 Hz), 1H), 3.65 (s, 3H), 163.88-161.09 (m), 3.57 (ddd, J = 8.5, 6.2, 2.6 Hz, 1H), 133.43-133.07 (m), 3.37 (dd, J = 8.5, 6.4 Hz, 1H), 124.58 (dd, J = 16.1, 3.24 (td, J = 8.9, 2.7 Hz, 1H), 4.1 Hz), 112.10 (dd, J = 20.8, 3.16-2.99 (m, 1H), 3.9 Hz), 2.87-2.68 (m, 1H), 2.51 (td, J = 14.2, 104.41 (t, J = 26.1 Hz), 84.49, 13.8, 11.6 Hz, 1H), 81.38, 77.43, 52.92, 2.43-2.21 (m, 1H), 1.95-1.25 (m, 47.12, 45.69, 32.01, 9H), 1.05 (dd, J = 5.4, 3.3 Hz, 30.33, 19.84, 19.81, 1H), 0.96 (d, J = 6.7 Hz, 3H), 19.38, 18.54, 18.42 0.96 (d, J = 6.7 Hz, 3H) ¹⁹F NMR (CD₃OD) δ 61.22 (d, J = 6.5 Hz), 61.11 (d, J = 6.6 Hz) F322 218-222 — ESIMS ¹H NMR (CD₃OD) δ 7.79 (dd, ¹³C NMR (CD₃OD) δ dec. m/z 480 J = 1.6, 0.6 Hz, 1H), 171.31, 163.00 (dd, J = 245.7, ([M + H]⁺) 7.28-7.22 (m, 1H), 7.19 (q, J = 8.3 Hz, 11.9 Hz), 1H), 6.79 (t, J = 8.9 Hz, 162.37 (dd, J = 246.5, 2H), 6.66-6.60 (m, 1H), 11.9 Hz), 159.59, 5.22-5.11 (m, 2H), 4.04 (dd, J = 10.9, 148.98, 144.99, 7.2 Hz, 1H), 2.72 (dd, J = 13.9, 133.20 (dd, J = 9.6, 6.4 Hz), 5.1 Hz, 1H), 2.56 (dd, 123.73 (dd, J = 15.7, J = 13.9, 9.6 Hz, 1H), 2.35 (dt, 3.8 Hz), 120.22, J = 13.3, 6.9 Hz, 1H), 113.23, 112.04 (dd, J = 21.2, 2.18 (dq, J = 9.0, 4.5 Hz, 1H), 3.7 Hz), 1.90-1.60 (m, 3H), 1.44 (q, J = 12.3, 104.43 (t, J = 26.1 Hz), 77.44, 11.8 Hz, 1H), 1.31 (d, J = 5.7 Hz, 75.47, 52.89, 43.74, 3H), 1.12-0.99 (m, 31.98, 31.03, 28.52, 1H) 19.19, 17.75 ¹⁹F NMR (CD₃OD) δ 61.51 (d, J = 6.8 Hz), 60.95 (d, J = 6.8 Hz) ¹H NMR were run at 400 MHz unless noted otherwise ¹³C NMR were run at 101 MHz unless noted otherwise ¹⁹F NMR were run at 376 MHz unless noted otherwise

TABLE 3 Biological Testing Rating Scale Rating Table for Fungal Pathogens % Control Rating 80 − 100 A More than 0 − Less than 80 B Not Tested C No activity noticed in this bioassay D

TABLE 4 Biological Activity - Disease Control in High and Low Volume Applications PUCCRT* SEPTTR* 1DP* 3DC* 1DP* 3DC* Rate Rate Cmpd. 121.5 100 121.5 100 121.5 100 121.5 100 No. g/H* ppm* g/H* ppm* g/H* ppm* g/H* ppm* F1 C A C B C A C A F2 C A C B C A C A F3 C A C A C A C A F4 C A C A C A C A F5 C A C B C A C A F6 C A C A C A C A F7 C A C B C A C A F8 C A C A C A C A F9 C A C A C A C A F10 A A B A A A A A F11 C A C B C A C A F12 C B C A C A C A F13 C D C B C A C A F14 C A C A C A C A F15 C A C A C A C A F16 C A C B C A C B F17 C A C B C A C A F18 C A C B C A C A F19 C A C A C A C A F20 C A C B C A C A F21 C A C A C B C B F22 C A C A C A C A F23 C A C A C A C A F24 C A C A C A C A F25 C A C D C A C B F26 C A C B C A C A F27 C A C A C A C A F28 C A C D C A C B F29 C C C C C C C C F30 C A C A C A C A F31 C A C A C A C A F32 C A C B C A C A F33 C A C A C A C A F34 C A C A C A C A F35 C B C D C A C D F36 C A C D C A C D F37 C B C B C A C D F38 C A C A C A C D F39 C A C A C A C B F40 C A C B C B C B F41 C A C B C A C A F42 C A C A C A C A F43 C A C A C A C A F44 C A C A C A C A F45 C A C A C A C A F46 C A C A C B C A F47 C A C A C A C A F48 C A C A C A C A F49 C A C B C A C A F50 C A C A C A C A F51 C A C B C A C B F52 C A C A C A C A F53 C A C A C A C B F54 C A C A C B C A F55 C A C D C A C B F56 C A C B C A C B F57 C A C A C A C B F58 C A C A C D C D F59 A A D A A A B A F60 A A D A A A D A F61 C A C B C A C D F62 A A B A A A A A F63 A A A A A A A A F64 A A A A A A A A F65 A A B A A A A A F66 B A B A A A B A F67 A A A A A A A A F68 A A B A A A A A F69 A A A A A A A A F70 A A A A A A A A F71 A A B A A A A A F72 A A B A A A A A F73 A A A A A A A A F74 A A B A A A A A F75 A A B A A A A A F76 A C A C A C A C F77 A A A A A A A A F78 A A A A A A A A F79 C A C A C A C A F80 A A A A A A A A F81 A A A A A A A A F82 A A A A A A A A F83 A A A A B A B D F84 A A A A B A D A F85 A C A C B C D C F86 A C A C A C A C F87 A C A C A C A C F88 A C A C A C A C F89 A A B A A A A A F90 A A A A A A A A F91 A A A A A A A A F92 A A A A A A A A F93 A A B A A A A A F94 C A C A C A C A F95 A A B A A A B A F96 A A B A A A A A F97 A A A A A A A A F98 A A A A A A A A F99 A A B A A A A A F100 A A B A A A A A F101 A A A A A A A A F102 A A B A A A A A F103 A A A A A A A A F104 A A B A A A A A F105 A D A A A A A A F106 A A A A A A A A F107 A A A A A A A A F108 A A B A A A A A F109 A A A A A A A A F110 A A A A A A A A F111 A C A C A C A C F112 A C A C A C A C F113 A A A A A A A A F114 A A B A A A A A F115 A A B A A A A A F116 A A A A A A A A F117 A A A A A A A A F118 A A A A A A A A F119 A A A A A A A A F120 A C D C A C B C F121 A A A A A A A A F122 A A A A A A A A F123 A A B A A A A A F124 A A A A A A A A F125 A A A A A A A A F126 A A B A A A A A F127 C A C A C A C A F128 A A A A A A A A F129 A A B A A A A A F130 A A A A A A A B F131 A A A A B A A A F132 A A A A A A A A F133 A A A A A A A A F134 C A C A C A C A F135 C A C A C A C A F136 A A A A A A A A F137 A A B A A A A A F138 A A A A A A A A F139 A A B A A A A A F140 A A A A B A B B F141 A A D B A A B A F142 A A A A A A B A F143 A A A A B B D B F144 A C D C A C B C F145 A C A C A C A C F146 A C A C A C A C F147 A A B A A A A A F148 A A A A A A A A F149 A A A A A A A A F150 A A B A A A A A F151 A A A A A A A A F152 A A A A A A A A F153 A A B A A A A A F154 A A A A A A A A F155 A A A A A A A A F156 A A A A B B B B F157 A C B C A C D C F158 A A B A A A A A F159 A A B A A A A A F160 A A A A A A A A F161 A A A A A A A A F162 A A B A A A A A F163 B A B B A A B A F164 A A B A A A A A F165 A A B A A A A A F166 A A A A A A A A F167 A A A A A A A A F168 A A A A A A A A F169 A A A A A A A B F170 A A B A A A A A F171 A A B A A A A A F172 A A A A A A A A F173 A A A A A A A A F174 A A A A A A A A F175 A A B A A A B A F176 A A B A A A A A F177 A A A A A A A A F178 A A B A A A A A F179 A A B A A A A A F180 A A B A A A A A F181 A A A A A A A A F182 A A B A A A A A F183 A A A A A A A A F184 C A C A C A C A F185 C A C A C A C A F186 C A C A C A C A F187 A A A A A A A A F188 A A A A A A A A F189 A A A A A A A A F190 A A B D A A A A F191 A A A A B A B D F192 A A A A D D D D F193 A C D C A C B C F194 A A B A A A A A F195 A A B A A A A A F196 A A A A B A B B F197 A C A C A C A C F198 A C A C A C A C *PUCCRT—Wheat Brown Rust (Puccinia triticina) *SEPTTR—Wheat Leaf Blotch (Septoria tritici) *1DP—1 Day Protectant *3DC—3 Day Curative

TABLE 5 Biological Activity—Disease Control at 100 ppm Compound. ALTESO* CERCBE* COLLLA* ERYSCI* ERYSGH* Number 1DP* F64 A A A A A F67 A A A B A F70 B A A A A F78 B A A B B F80 B A A D B F81 B A A B B F82 D A A D B F86 B A A D B F87 A A A B A F88 A A A A A F92 A A A A B F96 A A A A B F98 A A A A A F101 A A A A A F102 C C A C B F106 A A A A A F107 A A A A A F108 D A A D B F109 A A A A A F110 C C C C A F113 A A C A A F114 D A A D C F117 A A A A A F118 B A A B C F119 B A A A C F126 B A A A C F128 A A A B B F130 B B A B B F138 D A A D B F144 A B A B D F145 A A A A A F146 A A A D B F151 A A A A A F152 A A A A A F157 A A A D D F161 A A A A A F164 A A A A A F166 D D C D C F167 A A A A A F168 D D A D A F172 A A A A A F173 A A A A A F174 A A A A A F175 A A C B A F181 A B A B B F183 B B A B B F193 A A A D B 198 A A A A A *ALTESO—Tomato Early Blight (Alternaria solani) *CERCBE—Leaf Spot of Sugar Beets (Cercospora beticola) *COLLLA—Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotricum lagenarium) *ERYSCI—Powdery Mildew of Cucumber (Erysiphe cichoracearum) *ERYSGH—Barley Powdery Mildew (Blumeria graminis f.sp. hordei; Synonym: Erysiphe graminis f.sp. hordei) 1DP—1 Day Protectant

TABLE 6 Biological Activity - Disease Control at 100 ppm Compound. ERYSGT* LEPTNO* PYRIOR* RHYNSE* UNCINE* VENTIN* Number 1DP* F64 C A A A A B F67 C A A A B B F70 C A A A A B F78 C A A A B B F80 C C A D B B F81 C C A A A B F82 C C A B B B F86 C A A A A B F87 C A A A A C F88 C A A A A C F92 C A A A A A F96 C A A A A B F98 C A A A A B F101 C C A A A D F102 C C C C B C F106 A A A A A B F107 C C A A B C F108 C A A A A B F109 C A A A A A F110 C A A A A B F113 C C A A B C F114 C C A A C C F117 C A A A A A F118 C C A A C C F119 C C A A C C F126 C C A A C C F128 C A A B A B F130 C A A A B B F138 C C A B B B F144 C A C A B A F145 C A C A A A F146 C A A A A A F151 A A A C C B F152 C C A A B C F157 C A C A A B F161 C A A A A A F164 C A A A A A F166 C C D D C D F167 C C A A A A F168 C C D D A D F172 C A A A B B F173 C C A A B C F174 C A A A A A F175 C C A A B C F181 C A A B B D F183 C A A A A B F193 C A A A B A F198 C A A A A C *ERYSGT—Wheat Powdery Mildew (Blumeria graminis f.sp. tritici; Synonym: Erysiphe graminis f.sp. tritici) *LEPTNO—Wheat Glume Blotch (Leptosphaeria nodorum) *PYRIOR—Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae) *RHYNSE—Barley Scald (Rhyncosporium secalis) *UNCINE—Grape Powdery Mildew (Uncinula necator) *VENTIN—Apple Scab (Venturia inaequalis) *1DP—1 Day Protectant

TABLE 7 Biological Activity—Disease Control at 25 ppm Compound PHAKPA* Number 1DP* 3DC* F63 A A F64 A A F67 A B F70 A B F76 A A F78 A A F80 A B F81 A A F82 A A F86 A B F91 A A F92 A A F93 A B F96 A B F98 A A F101 A B F106 A B F107 A A F109 A B F113 A B F117 A A F118 A B F119 A B F121 A B F124 A A F128 A A F130 A A F132 A A F138 A A F144 B D F145 A B F146 A A F149 A B F151 A A F152 A A F155 A A F157 B D F160 A A F161 A A F164 A B F166 A B F167 A B F168 A B F172 A B F173 A A F174 A B F181 A A F183 A A F187 A A F189 A A 193 B B *PHAKPA—Asian Soybean Rust (Phakopsora pachyrhizi) *1DP—1 Day Protectant *3DC—3 Day Curative 

What is claimed is:
 1. A compound of Formula I

wherein: X is H; Y is Q; Q is

R₁ is chosen from H, alkyl, —CH₂—CH═CH₂, phenyl, or —C(O)R₆, each optionally substituted with 0, 1 or multiple R₆; R₂ is chosen from CH₂R₈, phenyl, alkyl, or —CH═CH₂, each optionally substituted with 0, 1, or multiple R₆, R₃ is chosen from alkyl, benzyl, or benzyloxy, each optionally substituted with 0, 1, or multiple R₅; R₄ is chosen from H, —C(O)R₇ or —CH₂OC(O)R₇; R₅ is chosen from alkyl, or halo; R₆ is chosen from alkyl, halo, haloalkyl, OCH₃, —O—CH₂-cyclopropyl, phenyl, 2-furanyl, —S—CH₃, or —C(O)R₅; R₇ is chosen from alkyl, —CH₂—CH₂—O—CH₃, or —CH₂—O—CH₂—CH₃, each optionally substituted with 0, 1, or multiple R₆; and R₈ is chosen from H, alkyl, or phenyl, each optionally substituted with 0, 1, or multiple R₆; wherein alkyl refers to a substituent selected from the group consisting of: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, branched or unbranched pentyl, branched or unbranched hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and wherein haloalkyl refers to an alkyl which is substituted with one or more of Cl, F, I, or Br, or a combination thereof.
 2. The compound according to claim 1, wherein R₁ is chosen from H, alkyl, phenyl, or —C(O)R₆, each optionally substituted with 0, 1 or multiple R₆.
 3. The compound according to claim 2, wherein R₂ is chosen from CH₂R₈, phenyl, or alkyl, each optionally substituted with 0, 1, or multiple R₆.
 4. The compound according to claim 3, wherein R₈ is chosen from H, alkyl, or phenyl, each optionally substituted with 0, 1, or multiple R₆.
 5. The compound according to claim 4, wherein R₄ is H, —C(O)R₇ or —CH₂OC(O)R₇.
 6. The compound according to claim 5, wherein R₄ is chosen from —C(O)R₇ or —CH₂OC(O)R₇.
 7. The compound according to claim 6, wherein R₇ is alkyl optionally substituted with 0, 1, or multiple R₆.
 8. A formulation for the control of a fungal pathogen, comprising: at least one of the compounds of claim 1; and a phytologically acceptable carrier material.
 9. The formulation according to claim 8, wherein the formulation is suitable for treating plants.
 10. A compound of Formula I,

wherein: X is H; Y is

R₁ is alkyl; R₂ is alkyl optionally substituted with 0, 1, or multiple R₆; R₄ is —CH₂OC(O)R₇; R₅ is alkyl or halo; R₆ is alkyl or phenyl; and R₇ is alkyl; wherein alkyl refers to a substituent selected from the group consisting of: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, branched or unbranched pentyl, branched or unbranched hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
 11. The compound of claim 10, wherein the compound is


12. A formulation for the control of a fungal pathogen, comprising: at least one of the compounds of claim 10; and a phytologically acceptable carrier material.
 13. The formulation according to claim 12, wherein the formulation is suitable for treating plants.
 14. A formulation for the control of a fungal pathogen, comprising: the compound of claim 11; and a phytologically acceptable carrier material.
 15. The formulation according to claim 14, wherein the formulation is suitable for treating plants. 